Wafer fabrication

ABSTRACT

Method and apparatus are set forth for providing a reactive radical species at a substrate surface. A wall structure defines an interior chamber. A substrate is mounted in the chamber at a target position therein with a surface region of the substrate oriented in a selected direction. A first vaporous chemical is introduced to the chamber with the first vaporous chemical flowing toward the surface region of the substrate. A first radical species is generated from the first vaporous chemical intermediate the position of introduction of the first vaporous chemical and the substrate surface region and at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species. The first radical species flows toward the surface region of the substrate. The chamber is evacuated and maintained at a pressure of ≦10 -7  Torr during the introduction of the first vaporous chemical. A second vaporous species may be introduced which reacts with the first radical species to produce a second radical species. Deposition, etching and cleaning can thereby be provided.

TECHNICAL FIELD

The present invention relates to an apparatus and a method for providing a reactive radical species at a substrate surface. The apparatus and method can serve for cleaning the surface, etching, with or without patterning, the surface, and deposition of layers on the surface of any desired thickness. The apparatus and method are particularly useful for the processing of semiconductor wafers but is also useful for coating objects for protective purposes and can further be used to grow crystalline objects such as diamonds.

BACKGROUND OF THE INVENTION

The semiconductor industry is continually attempting to develop smaller and finer delineations on the semiconductor devices and to, at the same time, increase the throughput of acceptable devices. There are a number of factors involved which effect the transferring onto wafers of contaminants. These include the use of high temperatures in wafer processing, the use of high electric fields near the surface, the use of liquids in contact with wafers during processing, the use of relatively high gas pressures (greater than one Torr), for example, during wafer processing and the handling of wafers by processing personnel.

At higher temperatures the mobility of contaminants in and on the wafer is greatly increased. Such elevated temperatures are used during epitaxy, diffusion and post-ion implantation annealing.

The use of high electrical fields near the wafer results in at least two types of problems. Charged particles on the surface have their mobilities greatly enhanced by the high fields. Furthermore, the high fields used in ion implantation and reactive ion etching impart large momenta to charged particles in the vicinity of the wafer. These large-momentum charged particles can drive surface contaminants into the wafer and can cause crystal damage to the wafer (as in the case of ion implantation). A crystal defect can be considered to be a contaminant or a set of contaminants relative to several semiconductor device functions.

Liquids are well known to exhibit a `bathtub ring` effect. This effect is the removing of a contaminant from one surface (or area on a surface) to another surface (or another area on the surface). Furthermore, dissolved materials in the liquid can deposit out on the surfaces in contact with the liquid.

When vapor phase chemistries are carried out on the surface of the wafer the by-products must be able to escape from the surface, or they will interfere with the desired chemistries, and they become trapped on the surface (or in the material being deposited when deposition chemistries are being used).

Finally, it is well-known that the `dirtiest things` in a clean room are the people in it. Some handling of wafers by people at this stage of development of wafer fabrication is unavoidable. It is, however, essential that this handling be minimized.

DISCLOSURE OF INVENTION

The present invention is directed to overcoming one or more of the problems as set forth above.

In accordance with an embodiment of the invention an apparatus is set forth for providing a reactive radical species at a substrate surface. The apparatus comprises a wall structure which defines an interior chamber. Mounting means serves for mounting a substrate in the chamber at a target position therein with a surface region of the substrate oriented in a selected direction. First vaporous chemical introducing means serves for introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface region of the substrate. First radical species generating means intermediate the first vaporous chemical introducing means and the substrate surface serves for generating a first radical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species with the first radical species flowing toward the surface region of the substrate. Pumping means serves for evacuating the chamber and for maintaining a pressure within the chamber of ≦10⁻⁷ Torr during the introduction of the first vaporous chemical.

In accordance with another embodiment of the invention a method is set forth for providing a reactive radical species at a substrate surface. The method comprises mounting a substrate in a sealed chamber at a target position therein with a surface region of the substrate oriented in a selected direction. A first vaporous chemical is introduced to the chamber with the first vaporous chemical flowing toward the surface region of the substrate. A first radical species is generated from the first vaporous chemical at a position in the chamber intermediate the place of introduction of the vaporous chemical and the surface region of the substrate without producing significant amounts of ionized species with the first radical species flowing toward the surface region of the substrate. The chamber is evacuated at a rate sufficient for maintaining a pressure within the chamber of 10⁻⁷ Torr or below during the introduction of the first vaporous chemical.

In accordance with another embodiment yet of the invention a method is set forth of cleaning a substrate to remove one or more solids or molecules from a surface thereof. The method comprises generating a neutral activated chemical species without generating a substantial quantity of ionized activated species at a pressure of no more than about 0.1 Torr within a sealed evacuatable chamber. The neutral activated chemical species is flowed against the surface, the neutral activated chemical species being selected to react with and convert at least one of the solids or molecules to a vaporous species. The chamber is evacuated at an evacuation rate sufficient to maintain the pressure therein at ≦10⁻⁷ Torr during the flowing until a desired quantity of the solid or molecules has been removed by vaporization.

Another embodiment still of the invention is a method of etching into a surface of a substrate. The method comprises generating a neutral activated chemical species without generating a substantial quantity of ionized activated species at a pressure of no more than about 0.1 Torr within a sealed evacuatable chamber. The neutral activated chemical species is contacted with the surface, the neutral activated chemical species being selected to react with and convert the surface to a vaporous species until a desired quantity of the surface has been removed by vaporization. The chamber is evacuated at an evacuation rate sufficient to maintain the pressure therein at ≦10⁻⁷ Torr during the flowing until a desired quantity of the surface has been removed by vaporization.

An embodiment of the invention provides a method of depositing a chemical species on the a surface region of a substrate. The method comprises mounting a substrate in a sealed chamber at a target position therein with the surface region of the substrate oriented in a selected direction. A first vaporous chemical is introduced to the chamber with the first vaporous chemical flowing toward the surface region of the substrate. A first radical species is generated from the first vaporous chemical at a position in the chamber intermediate the place of introduction of the vaporous chemical and the surface region of the substrate without producing significant amounts of ionized species with the first radical species flowing toward the surface region of the substrate. The chamber is evacuated at a rate sufficient for maintaining a pressure within the chamber of 10⁻⁷ Torr or below during the introduction of the first vaporous chemical. A second vaporous chemical is introduced to the chamber intermediate the position of generation of the first radical species and the surface region of the substrate. The second vaporous chemical flows toward the surface region of the substrate. The second vaporous chemical is selected to react with the first radical species such that substantially all of the second vaporous chemical reacts with the first radical species to produce a second radical species flowing toward the surface region of the substrate. The second radical species, on contacting the surface region of the substrate, deposits the chemical species.

The present invention makes use of very far from thermodynamic equilibrium (VFFTE) chemistries thereby minimizing or avoiding entirely the above-mentioned problems of the prior art. With VFFTE chemistries heating of the wafers are not required; no charged particles are used in the vicinity of the wafers; no liquids are used; only total gas pressures below one Torr are used; and handling of wafers by people is minimized.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be better understood by reference to the Figures of the drawings wherein:

FIG. 1 illustrates, schematically, an apparatus in accordance with an embodiment of the invention which is suitable for carrying out methods in accordance with embodiments of the invention; and

FIG. 2 illustrates, graphically, equilibrium and very far from equilibrium (VFFE) energy/entropy relationships;

Illustration 3 (which is a part of the text rather than a separate drawing) illustrates, schematically, energy levels and energy interactions.

BEST MODE FOR CARRYING OUT INVENTION

Microwave generators are useful in certain embodiments of the invention. Microwave generators useful in the accordance with the present invention will generally be operated at less than the avalanche mode of operation. The frequency is not critical. Typically, commercial 2.45 Gigahertz microwave generators can be utilized. They generally will have a power above one kilowatt and at times as much as or even more than 20 kilowatts. The current will be generally low, for example, no more than 2 amperes. The electron energy is kept low enough so that substantially no ionic species are formed. Instead, only radical species are formed. When electron guns are utilized in accordance with various embodiments of the present invention they are generally utilized at a maximum of about 20 volts since at higher voltages ionization would occur. Typically the electron gun would operate at relatively high amperage, normally from 3 to 1,000 amps.

When tunable lasers are utilized, they are generally subject to the same parameters as are the electron guns. Typically they will be operated at a wavelength which falls within a range from about 600 to about 3,000 Angstroms.

When either electron guns or lasers are utilized, they are preferably utilized in a symmetrically placed mode preferably with an odd number of electron guns or tunable lasers, the electron guns being positioned so as to provide a relatively even sweep of energy across the chemical species being introduced whereby the activated species impinging on the wafer surface are relatively evenly distributed over the entire surface of the wafer.

Chemicals introduced can be utilized as diluents, as reactants with surface species or as sources of secondary radicals formed by the reaction of the primary radicals formed in the neutral activated species generating portion of the vacuum chamber. In the latter instance substantially all of the species impinging on the surface of the substrate will be in the nature of secondary radicals produced by reaction of the initial activated species with the vaporous chemical being introduced nearer the target, possibly with some excess of the first radical species also being present. If the chemicals introduced serve as reactants with surface species they will arrive at the surface along with the primary radicals. Diluents are useful in removing photoresists and the like so as to moderate the reaction with the primary radicals.

In operation a substrate is mounted in a sealed chamber at a target position therein with a surface region of the substrate oriented in a selected direction. A first vaporous chemical is introduced to the chamber with the first vaporous chemical flowing toward the surface region of the substrate. In the particular embodiment illustrated this would occur at an upper chemical introduction circle. A first radical species is generated from the first vaporous chemical at a position in the chamber intermediate the place of introduction the vaporous chemical and the surface region of the substrate without producing significant amounts of ionized species with the first radical species flowing toward the surface region of the substrate. The chamber is evacuated at a rate sufficient for maintaining a pressure within the chamber of 10⁻⁷ Torr or below during the introduction of the first vaporous chemical.

As mentioned above, a second vaporous chemical can be introduced to the chamber intermediate the position of generation of the first radical species and the surface region of the substrate, with the second vaporous chemical flowing toward the surface region of the substrate, the second vaporous chemical being selected to react with the first radical species to produce a second radical species flowing towards the surface region of the substrate. The geometry of introduction of the first vaporous chemical and the geometry of the first species generating means is preferably such as to provide substantial uniform distribution of the second radical species over the surface region of the substrate.

The specific spacing and positioning of the upper circle, a lower circle at which the second vaporous species can be introduced, the wafer and even the walls of the vacuum chamber can be important to the practice invention. When a microwave cavity is utilized to produce the first activated species the microwave cavity will generally be in the region between the upper and the lower circles or rings, a distance of 3 to 6 inches. The distance between the lower ring to the wafer surface will generally be from about 6 inches to about 12 inches. Generally the width of the chamber should be about three times of the diameter of the wafer being treated. This, along with the high pumping rate provided, serves to assure that the surface of the wafer will be relatively uniformly impinged upon by the activated or radical species.

FIG. 1 illustrates an apparatus 10 in accordance with an embodiment of the invention. The apparatus 10 includes a wall structure 12 which defines an interior chamber 14 accessible via an evacuatable entry port 13. Mounting means 16, in the embodiment illustrated a platform 18, serves for mounting a substrate 20, suitably a semiconductor wafer, in the chamber 14 at a target position 22 therein with a surface region 24 of the substrate 20 oriented in a selected direction (upwardly in the particular environment illustrated but the orientation is arbitrary and the direction which gravity acts is not important to the invention).

First vaporous chemical introducing means 26, in the embodiment illustrated an upper ring 28 having a plurality of holes 30, is located within the chamber 14 and is oriented to direct the first vaporous species toward the surface region 24 of the substrate 20. In the particular embodiment illustrated the holes 30 are evenly spaced about the ring 28 to provide as even a flow and as uniform a distribution as possible of vaporous species over the surface region 24 of the substrate 20.

First radical species generating means 32 is provided intermediate the first vaporous species introducing means 26 and the substrate surface region 24. The first radical species generating means 32 serves for generating a first radical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts, and preferably zero, of ionized species with the first radical species flowing toward the surface region 24 of the substrate 20.

There are several alternatives for providing generation of the first radical species. For example, the first radical species generating means may be, or may include, a microwave generator 34 along with a microwave cavity 35 defined by walls 37. The microwave generator 34 may be used in combination with a defocussed electron gun and power supply 36. One or more additional defocussed electron guns 38 may be present. Also, and in what is a preferred embodiment, a plurality of defocussed electron guns 36,38 may be utilized without the microwave generator 34 (and without the microwave cavity walls 37). Instead of, or in addition to the electron guns, one can provide a β-emitter, for example, a nickel β-emitter, positioned so as to provide electrons in the cavity 35. The β-emitter can be present in elemental or combined form. The result will be a less expensive but generally less efficient apparatus. As still another embodiment useful alone or in combination with the microwave generator 34 and the defocussed electron gun 36 or guns 36,38, a defocussed laser and power supply 40, generally a tunable laser, may be used to generate the first radical species. The location of the first radical generating means 32 and the location and orientation of the first vaporous species introducing means 26 are such as to provide a substantially uniform distribution of the first radical species over the surface region 24 of the substrate 20.

In accordance with a preferred embodiment of the invention the chamber 14, where the substrate 20 is mounted, is at least about three times the width of the largest cross-dimension of the surface region 24.

In accordance with an embodiment and certain uses and methods of the invention it may be desirable or necessary to introduce a second vaporous species between the first radical species generating means 32 and the surface region 24 of the substrate 20. In such instances second vaporous chemical introducing means 42 is provided for introducing the second vaporous species intermediate the first radical species generating means 32 and the surface region 24 of the substrate 20. The second vaporous species is flowed towards the surface region 24 of the substrate 20. It is selected to react with the first radical species to produce a second radical species flowing toward the surface region 24 of the substrate 20. In the particular embodiment illustrated the second vaporous species introducing means 42 is similar in construction to the first vaporous species introducing means 26. More particularly, it includes a ring 44 with a plurality of oriented holes 46. When two vaporous species introducing means are present in the desired orientation it becomes possible to select and use a first vaporous species which can readily form the first radical species and, through reaction of the first radical species with the second vaporous species, to produce a second radical species which could not be readily directly produced by radical species generating means alone, i.e., by defocussed electron guns, defocussed lasers and/or microwave generators.

Means 48 is provided for evacuating the chamber 14 at a rate sufficient for maintaining a pressure within the chamber of 10⁻⁷ Torr or below during the introduction of the first vaporous species. In the particular environment illustrated the evacuating means 48 is in the nature of a high speed pump 50. Relatively large conduits 52 lead from the chamber 14 to the pump 50. Preferably, the conduits 52 open onto openings 54 which are located about and downstream from the substrate 20 whereby vaporous species generated at and/or flowing past the substrate 20 are efficiently carried through the large openings 54 and the large conduits 52 to the high speed pump 50.

The invention provides a number of capabilities. For example, a radical species can be produced which can carry out a chemical reaction on the surface region 24 of the substrate 20. Deposition of a chemical can be carried out in this manner. If desired, the radical species can be used to clean (remove one or more solids from) the surface 24 of the substrate 20. The surface region 24 of the substrate 20 can be etched using this technique. This can be done in connection with etching techniques such as masking to provide a desired etching pattern. An advantage of the apparatus and method of the invention is that a single apparatus can be used in sequential steps to carry out different chemistries. For example, a selected radical species, e.g., atomic hydrogen, may be generated for a time sufficient to clean the surface 24 of the substrate 20. Thereafter, through introducing one or more different vaporous chemicals thereby changing the first and/or second radical species, deposition can proceed in the same apparatus without changing the substrate or its orientation.

The composition of the gaseous species being evacuated from the chamber 14 can be monitored by monitoring means 56 which can include a probe 58 which is positioned in the chamber 14 adjacent the openings 54. The monitoring means 56 can utilize any convenient analytical technique, e.g., mass spectroscopy, gas chromatography or visible, laser fluorescent spectroscopy, ultraviolet or infrared spectroscopy. In the Figure a laser 60 powered by a power source (not shown) can provide a laser beam 63, shown in phantom, across and above the surface 24 of the substrate 20 and a detector 62 located at 90° from the direction of the laser beam along with an optical spectrometer 64 for monitoring the chemical reactions. When the composition being monitored changes such can be used as an indication or determinant that the desired layer has been fully or sufficiently removed.

II. THERMODYNAMICS A. Equilibrium Thermodynamics

In Classical Thermodynamics the First Law (The Conservation of Energy) is written

    dE=q+w,                                                    [I-1]

where dE is the differential change in the internal energy of the system, q is an infinitesimal amount of work done by the environment on the system. (In the earlier literature the convention used was that of the work done by the system rather than on the system. Thus, [I-1] was formerly written dE=q-w.) Although dE is an exact differential (independent of path), q and w may not be. It is therefore desirable to define the paths in ways such that dE is expressible in terms of exact differentials. There are several ways in which this can be done. q can be replaced with C dT, where C is the heat capacity, and T is the absolute temperature. (It will be convenient to represent extensive variables--those proportional to the amount of matter in the system--in bold print and intensive variables--those not proportional to the amount of matter in the system--in ordinary print). w can be replaced by a₁ dA₁ +a₂ dA₂ +. . . +a_(n) dA_(n) where a₁ is an intensive variable such as pressure, a mechanical force, the electromotive force, the magnetic field or a chemical potential; and A₁ is the associated extensive variable such as volume, distance, the electric charge, the magnetization or the number of moles of a chemical species, respectively. Using the Einstein summation convention we can now write [I-1] as ##EQU1## Equation [I-2] has two peculiarities. The first differential on the right side of the equation is that of an intensive variable, whereas all the other n+1 differentials are those of extensive variables, and there is no intensive variable associated with the internal energy.

We shall define a new extensive variable,

    dS=CdT/T                                                   [I-3]

called `Entropy`. We can now rewrite [I-2] as ##EQU2## Recognizing that integers are intensive variables, we can rewrite [I-4] as ##EQU3## where d/A_(o) =dE and a₀ =-1. At the first blush [I-5] looks strange. The right hand side is the sum of products of intensive variables and their associated extensive variables. The left hand side is simply zero, an integer. The answer to this apparent inconsistency is that the a₁ 's are the elements of a vector. The dA₁ 's are the elements of a second vector which is orthogonal to the first vector. Hence, their scalar product is zero. Although [I-5] has some interesting mathematical consequence, [I-4] is more useful for the present discussion.

We shall consider a closed system which is of constant volume and is surrounded by an `energy controlling` bath. Traditionally a closed system is defined as one for which energy can be transferred between the system and the environment, but mass cannot be transferred. By Relativity, however, energy and mass are two different facets of the same entity. Thus, the traditional definition of a closed system is `leaky`. We shall, therefore, define a closed system as one for which only zero rest mass particles can be transferred between the system and the environment.

Traditionally the environment here would be called a `temperature controlling` or `temperature controlled` bath. Since, as we shall show temperature is not always defined, we prefer the appellation `energy controlling`. (If one wishes to be strictly accurate, one should note that an `energy controlling` bath is not the same as a `temperature controlling` bath. With a `temperature controlling` bath a system can undergo a phase transition during which the temperature of the system does not change, but the energy does. With an `energy controlling` bath a phase change cannot occur unless the bath is reset to allow the net transfer of energy between the system and the bath.) At equilibrium

    a.sub.1 dA.sub.i =0 (at equilibrium), (i summed from 1 to n),[I-6]

and

    dS/dE=1/T[I-7]

(For near-equilibrium conditions we should use the partial derivative with the notation that all of the A₁ 's of [I-6] are held constant). In FIG. 2, the curve labelled `EQUILIBRIUM CURVE` represents [I-7] with the acknowledgement of the Third law requirement that entropy start at the value of zero, and with the acknowledgement that Relativity and Quantum Mechanics require that the internal energy start at a value greater than zero. We shall return to FIG. 2 when we discuss Non-Equilibrium Thermodynamics. Returning now to [I-4], we can rewrite the equation as

    dE-TdS=a.sub.1 dA.sub.1 (i summed from 1 to n)             [I-8]

We now define a new extensive variable, A_(H), such that

    dA.sub.H =dE-TdS                                           [I-9]

A_(H) is the `Helmholtz Free Energy`. It is standardly represented by `A`. We have appended the H subscript in order to distinguish it from the other A₁ 's. Substituting [I-9] into [I-8] we obtain

    dA.sub.H =a.sub.1 a.sub.1 dA.sub.1 (1 summed from 1 to n)  [I-10]

By virtue of [I-6]

    dA.sub.H =0 (at equilibrium)                               [I-11]

One of the terms on the right hand side of [I-10] is PdV_(e), where P is the pressure of the system and V_(e) is the volume of the environment. Since

    dV.sub.s =-dV.sub.e

where V_(s) is the volume of the system, we can rewrite [I-10] as

    dA.sub.H =-PdV.sub.s +a.sub.1 dAi (i summed from 2 to n).

It is traditional to define A_(H) for constant volume conditions. Thus,

    dA.sub.H =a.sub.1 dA.sub.1 (dV.sub.s =0) (i summed from 2 to n)[I-13]

Since so much chemistry is carried out under constant pressure rather than constant volume conditions, it is convenient to introduce two more extensive variables, H-`Enthalpy`, and G-`Free Enthalpy`, more usually called `Gibbs Free Energy`, by ##EQU4## From [I-9], [I-12] and [I-15] we obtain

    dG=a.sub.1 dA.sub.1 (i summed from 2 to n)                 [I-16]

For constant pressure conditions the requirement for equilibrium is

    a.sub.1 dA.sub.1 =0 (at equilibrium, constant pressure) (i summed from 2 to n)                                                        [I-17]

Thus,

    dG=0 (at equilibrium, constant pressure)                   [I-18]

Standardly, it is ΔH, ΔG and S (constant pressure) which are measured and tabulated, rather than ΔE, ΔA_(H) and S (constant volume). If we restrict our considerations to systems at low pressures, the ideal gas law,

    PV=nRT                                                     [I-19]

or

    PΔV=ΔnRT (constant P,T)                        [I-20]

is applicable. For vapor phase reactions for which the sum of the number of reactant molecules is equal to the sum of the number of product molecules, Δn=0, and hence PAY=0. Thus,

    ΔH=ΔE (Δn=0)                             [I-21]

We can therefore, use the data of the standard tabulations of ΔH_(f) ⁰ '(standard Enthalpies of formation), to calculate the ΔE_(r) ⁰ 's (standard Internal Energies of reaction) of reaction for which An=0.

From Equilibrium Statistical Mechanics, using the Principle of the Equipartition of Energy, we can obtain at equilibrium

    {[N(j)/g(j)]/[N(i)/g(i)]}exp [ΔH(ji)/kT]=1,          [I-22]

where N(j) is the number of items under discussion in states for which the enthalpy is ΔH(J), g(j) is the number of such states (the `multiplicity`), k is the Boltzmann constant, T is the absolute temperature and ΔR(ji) is the change in enthalpy of the item in going from one of the i-th states to one of the j-th states. For the purposes of [I-22] it is assumed that

    ΔH(ji)>0.                                            [I-23]

Since the exponential term in [I-22] is positive definite by virtue of [I-23], it follows that

    N(j)/g(j)<N(i)/g(i)                                        [I-24]

for all values of T. In order that

    N(j)/g(j)>N(i)/g(i)                                        [I-25]

T would have to be negative. This cannot, however, be the case since T is an absolute temperature. In VFFTE systems such as those which we shall be discussing later, [I-25] is the case. Thus, we must conclude that temperature is not defined for VFFTE systems.

Equation [I-22] can be rearranged to a more familiar form.

    [N(j)/g(j)]=[N(i)/g(i)]exp [-ΔH(hi)/kT],

or

    [N(j)/N(i)]=[g(j)/g(i)]exp[-ΔH(ji)/kT].

Let

    S(j)=k ln [g(j)]                                           [I-26]

    ΔS(ji)=ΔS(j)-ΔS(i)                       [I-27]

and

    K(ji)=N(j)/N(i)                                            [I-28]

Using the definition of the Gibbs Free Energy, [I-15], we have

    K(ji)=exp[-ΔG(hi)/kT]                                [I-29]

(The reader may be surprised to find an extensive variable `sitting by itself` in [I-22], [I-26] and I-29]. This is because the Boltzmann constant's units are J/K/molecule. It, thus, is an `extensive constant`. Equation [I-26] is the equation developed by Max Karl Ernst Ludwig Planck in his work on the `Black Body Problem` for which he invented the constant `k`, which is known as `Boltzmann's Constant` rather than `Planck's Constant`. The appellation `Planck's constant`, of course, is reserved for `h`--the quantum of action. Planck invented h in his work on the `Black Body Problem`.)

B. VFFTE Thermodynamics

Although equilibrium thermodynamics can be, and is, applied to near-equilibrium systems, it cannot be applied to VFFTE systems. The discussion of [I-22] showed that T is not defined for VFFTE systems. If T is not defined, then by virtue of [I-19] P is not defined. If it were, then by [I-19] we could define T. Similarly, A_(H), H and G--by virtue of [I-9], [I-14] and [I-15], respectively--cannot be defined. We are, thus, left with only E, S, V and the N(j)'s for VFFTE systems.

Some very `strange` things happen in VFFTE systems. Let us consider, as a simple example, a system with three energy levels and three items which can be in any of the three energy states (cf. ILLUSTRATION 3]. As we did relative to ILLUSTRATION 2, we shall assume that the system has a constant volume and is in an energy-controlled bath. The energy levels have the energy values E₁ =0, E₂ =1 and E₃ =2. We start with all three items in the E₃ state. E=6 and g=1. By [I-26], if g=1, S=0. We now stepwise remove one unit of energy. We must consider two Cases--the items are distinquishable and the items are indistinguishable.

    __________________________________________________________________________     ILLUSTRATION 3                                                                 E.sub.3 = 2                                                                        X.sub.1                                                                          X.sub.2                                                                          X.sub.3     X.sub.2                                                                          X.sub.3                                                                           X.sub.1                                                                            X.sub.3                                                                           X.sub.1                                                                          X.sub.2                                      E.sub.2 = 1       X.sub.1  X.sub.2  X.sub.3                                    E.sub.1 = 0                                                                    E = 6                    E = 5                                                 g = 1(1)*                g = 3(1)*                                             (a)                      (b)                                                         X.sub.2                                                                          X.sub.3                                                                           X.sub.1                                                                            X.sub.3                                                                           X.sub.1                                                                          X.sub.2                                                                             X.sub.1  X.sub.2  X.sub.3                                                        X.sub.2                                                                          X.sub.3                                                                           X.sub.1                                                                            X.sub.3                                                                           X.sub.1                                                                          X.sub.2                               X.sub.1      X.sub.2  X.sub.3                                                                    E = 4                                                                          g = 6(2)*                                                                      (c)                                                                  X.sub.3                                                                             X.sub.2  X.sub.3                                                                           X.sub.1  X.sub.2                                                                             X.sub.1                                       X.sub.2  X.sub.3                                                                           X.sub.1    X.sub.3                                                                           X.sub.1  X.sub.2                               X.sub.1    X.sub.1  X.sub.2                                                                               X.sub.2  X.sub.3                                                                               X.sub.3                                               E = 3                                                                          g = 6(2)*                                                                      (d)                                                                X.sub.2                                                                          X.sub.3                                                                           X.sub.1                                                                            X.sub.3                                                                           X.sub.1                                                                          X.sub.2                                                                             X.sub.1  X.sub.2  X.sub.3                             X.sub.1      X.sub.2  X.sub.3                                                                             X.sub.2                                                                          X.sub.3                                                                           X.sub.1                                                                            X.sub.3                                                                           X.sub.1                                                                          X.sub.2                                          E = 2                E = 1                                                     g = 3(1)*            g = 3(1)*                                                 (e)                  (f)                                                              X.sub.1                                                                          X.sub.2                                                                          X.sub.3                                                                    E = 0                                                                          g = 1(1)*                                                                      (g)                                                          ILLUSTRATION 3 E                                                                        g                                                                              DISTINGUISHABLE ITEMS                                                                          INDISTINGUISHABLE ITEMS                               __________________________________________________________________________     (a) 6    1               1                                                     (b) 5    3               1                                                     (c) 4    6               2                                                     (c) 4    6               2                                                     (d) 3    6               2                                                     (e) 2    3               1                                                     (f) 1    3               1                                                     __________________________________________________________________________      (*g values in parentheses are for indistinguishable items)               

In either case as the energy of the system is reduced the entropy increases initially reaches a maximum value, and then decreases. This is not the behavior which we noted for equilibrium systems (FIG. 2. EQUILIBRIUM CURVE). There we observed a decrease in the entropy with any decrease in the internal energy.

Consider the point A in FIG. 2. The system is near equilibrium. Holding the energy of the system constant, we find that the entropy of the system increases until it reaches the equilibrium value. Now consider the point B. Here we have a VFFTE system like that in ILLUSTRATION 3. Holding the energy of the system constant, we find that nothing happens. The entropy does not change! There is no mechanism available by which it can. As we lower the energy of the system the entropy follows the `VFFTE CURVE`. When the energy has lowered sufficiently, the curve joints the `EQUILIBRIUM CURVE`. Of course, not all systems are like that of ILLUSTRATION 3. The `trick` is to choose those systems and conditions so that the system will follow the `VFFTE CURVE`. Before we consider how to make such choices, we must discuss first some of the factors involved in the kinetics of chemical reactions.

III. CHEMICAL REACTION KINETICS A. Absolute Reaction Rate Theory

Absolute Reaction Rate Theory is also known in the literature as `Activated Complex Theory` and Transition State Theory`. In order to clarify the use of these different terms let us consider a simple model reaction.

    A+B→C+D                                             [I-30]

It is assumed that the reactants combine for a short period of time to form the `activated complex` AB.sup. which then decomposes to form the products. Thus, [I - 30 ] is written

    A+B→AB.sup. →C+D                             [I-30a]

It is further assumed that the reactants are in equilibrium with the activated complex, or--more accurately--that the reactions

    A+B→AB.sup.

and

    AB.sup. →A+B

are fast compared with

    AB.sup. →C+D

Thus, [I-30a] becomes

    A+B=AB →C+D                                         [I-30b]

If we consider traditional chemical kinetics, we can write ##EQU5## where the square brackets here indicate concentrations (and not equation numbers), t is time and k_(r) is the rate constant. The rate with which AB.sup. decomposes is equal to [AB.sup. ] times a frequency term, kT/h, where k is Boltzmann's constant, T is the absolute temperature and h is Planck's constant. We shall not prove here that kT/h is the correct frequency term because of the complexities of the proof which involves concepts from statistical quantum mechanics. Thus, we can also write ##EQU6## where K.sup. is the `equilibrium constant`, we can combine [I-31] and [I-32] to obtain ##EQU7##

From the viewpoint of dimensional analysis [I-34] appears to be in error. The dimensionality of k_(r) appears to be time⁻¹, but in [I-31] its dimensionality is concentration⁻¹ time⁻¹. Going back to the derivation of [I-29] we see that [I-34] really should have been written ##EQU8## where ΔH.sup. is the enthalpy of activation. Since the g's are proportional to concentrations, the dimensionality of g (AB)/9(A)g(B) is concentration⁻¹. This fact is hidden by [I-26] in which g is treated as though it were dimensionless. By virtue of entropy being an extensive variable, g must be proportional to the amount of material. Thus, [I-34] is valid whether the reaction is unimolecular, bimolecular, trimolecular, etc.

At the thermodynamic equilibrium the principle of the equipartition of energy applies. Each translational and rotational degree of freedom `receives` kT/2 as its energy `allotment`. Each vibrational degree of freedom `receives` a `double allotment`, kT. This is because a vibrational degree of freedom is actually two--a kinetic energy degree of freedom and a potential energy degree of freedom. Let W be the total amount of energy available in the system, and n be the number of degrees of freedom, then at equilibrium

    W=nkT/2                                                    [I-36]

and

    kT=2W/n                                                    [I-37]

Under VFFTE conditions W is not equipartitioned among all degrees of freedom. It is restricted to just a few degrees of freedom. Let us assume that there are p such degrees of freedom where

and define

    p<<n                                                       [I-38]

    q=2/p,                                                     [I-39]

then ##EQU9## and

    qW>>kT.                                                    [I-40]

Since T and ΔH are not defined under VFFTE conditions, we must rewrite [I-34] as ##EQU10## By virtue of [I-40] the first factor on the right is much greater than the corresponding factor in [I-35]. The second factors in the two equations are essentially equal. There is a small difference between ΔS under constant pressure conditions and ΔS under constant volume conditions. The third factor in [I-41] is much greater than that in [I-35] even when the difference between ΔH and ΔE is taken into account. Thus, a reaction will be much faster under VFFTE conditions than under Near Thermodynamic Equilibrium (NTE) conditions.

Since under NTE conditions W is partitioned among many degrees of freedom, it is possible for several different reaction paths to have sufficient activation energy (or enthalpy) for reactions to occur. As a result several other products besides the desired one may be produced. The desired product is, therefore, contaminated by these other products. If the purity of the desired product is crucial for its intended use, the presence of these contaminants can be a very serious problem.

If the system is properly prepared for the VFFTE reaction, all or most of W will be in the degree (or degrees) of freedom which will lead to the desired product. Thus, the product will be produced much purer than that produced under NTE conditions as well as being produced much faster. (How to prepare the system properly for the VFFTE reaction may not be obvious and may require a considerable amount of ingenuity.)

Let us consider a specific example of these principles. Suppose that we wish to generate methyl radicals from methane. We could use dioxygen or monoxygen as the oxidant.

    ______________________________________                                         [I-42]                                                                              CH.sub.4 (g) + O.sub.2 (g) → CH.sub.3 (g) + HO.sub.2 (g)           -51      O      148     14, ΔG.sub.r.sup.0 (298 K.) = +213 kJ                                   mol.sup.-1,                                             or                                                                             [I-43]                                                                              CH.sub.4 (g) + O(g) → CH.sub.3 (g) + OH(g)                         -51      232    148     34, ΔG.sub.r.sup.0 (298 K.) = +1 kJ                                     mol.sup.-1,                                             followed by                                                                    [I-44]                                                                              CH.sub.4 (g) + HO.sub.2 (g) → CH.sub.3 (g) + HO.sub.2 (g)          -51      14     148    -105, ΔG.sub.r.sup.0 (298 K.) = +80 kJ                                   mol.sup.-1,                                             or                                                                             [I-45]                                                                              CH.sub.4 (g) + OH(g) → CH.sub.3 (g)+ H.sub.2 O(g)                  -51      34     148    -229, ΔG.sub.r.sup.0 (298 K.) = -64 kJ                                   mol.sup.-1.                                             ______________________________________                                           (Note:                                                                        All thermodynamic data are from Reference (A) unless the Reference is          specifically stated.) Thus, we see that the monoxygen reaction is more         exoergonic than the dioxygen reaction, and the follow up reaction from th      monoxygen reaction (the OH reaction) is, more exoergonic than the follow       up reaction from the dioxygen reaction (the HO.sub.2 reaction).          

For a proposed chemical reaction to be useful it must be thermodynamically permitted and kinetically favorable. The greater the exo-ergonicity (and/or the exo-thermicity) of a chemical reaction is, the more likely it is that the reaction will be fast. This is, of course, not a guarantee. It is, however, guaranteed that a reaction which is highly endo-ergonic (and/or endothermic) will be very slow. As a test of this Principle let us look at the rate constants for these four reactions. The data are taken from <I-1>.

    k[I-42]=6.67×10.sup.-11 exp(-28,640/T)cm.sup.3 molecule .sup.-1 s.sup.-1,                                                 [I-46]

    k[I-43]=1.7×10.sup.-15 T.sup.15 exp(-4,330/T)cm.sup.3 molecule.sup.-1 s.sup.-1,                                                 [I-47]

    k[I-44]=3.0×10.sup.-13 exp(-9,350/T)cm.sup.3 molecule.sup.-1 s.sup.-1[I- 48]

and

    k[I-45]=3.2×10.sup.-19 T.sup.24 exp(-1,060/T)cm.sup.3 molecule.sup.-1 s.sup.-1.                                                 [I-49]

    k([I-42], 298K)=1.22×10.sup.-52 cm.sup.3 molecule.sup.-1 s.sup.-1,

    k([I-43], 298K)=4.3×10.sup.-18 cm.sup.3 molecule.sup.-1 s.sup.-1,

    k([I-44], 298K)=7.1×10.sup.-27 cm.sup.3 molecule.sup.-1 s.sup.-1

and

    k(I-45],298K)=7.9×10.sup.-15 cm.sup.3 molecule.sup.-1 s.sup.-1.

Thus we find that the Principle holds for this case.

By raising the temperature of the system for [I-42] the reaction rate of [I-43] can be attained. What is the required temperature?

    k([I-42],T)=k([I-43], 287K)

    6.7×10.sup.-11 exp(-28,640/T)=4.3×10.sup.-18

    T=1729K.

While specialized equipment is required to operate at so high a temperature, it can be done. At so high a temperature, however, numerous side reactions can be expected to occur. For example, for the reaction

    CH.sub.4 (g)=C(graphite)+2H.sub.2 (g)                      [I-50]

    K.sub.r ([I-50], 1700K)=975                                [I-51]

Thus, at equilibrium only about 0.1% of the carbon is in the form of methane. The vast majority of the carbon has been deposited on the surfaces of the reactor. Since ΔG_(f) ⁰ (C, g, 4600K)=+0.5kJ mol⁻¹, there will also be a negligible quantity of carbon vapor at 1729K.

Since ΔH_(f) ⁰ (O, g, 298K)=+249 kJ mol⁻¹, a significant amount of energy, we should also consider how much energy is required to heat the methane and dioxygen from 298K to 1729K. The proper way in which to calculate these quantities is to integrate C_(p) with respect to T from 298K to 1729K. A simple way to approximate these quantities is to multiply the average value of C_(p) over the temperature range by the temperature range. Thus, ##EQU11## The factor of 10⁻³ is present because heat capacities are usually given in J mol⁻¹ K⁻¹. Similarly, ##EQU12## To these two energy requirements we must add the energy required to heat the reactor from 298K to 1729K. Although iron melts at 1809K, let us assume that the reactor is made of 100 gram atoms of iron (around twelve pounds). ##EQU13## where 0.9 kJ/gram atom and 0.8 kJ/gram atom are the heats of transition from the alpha phase to the gamma phase and from the gamma phase to the delta phase, respectively. Thus, although it requires more energy to generate the monoxygen than is required to heat the methane and dioxygen from 298K to 1729K, the monoxygen requirement is quite small when the total 1729K energy requirement is considered.

As another example, let us consider the generation of formyl from formaldehyde. Again the kinetic data are from <I-1>.

    ______________________________________                                         [I-55]                                                                              HCHO(g) + O.sub.2 (g) → CHO(g) + HO.sub.2 (g)                      -110     0      28      14, ΔG.sub.r.sup.0 (298 K.) = +152 kJ                                  mol.sup.-1,                                              [I-56]                                                                              HCHO(g) + O(g) → CHO(g) + OH(g)                                    -110     232    28      34, ΔG.sub.r.sup.0 (298 K.) = -60 kJ                                   mol.sup.-1,                                              [I-57]                                                                              HCHO(g) + HO.sub.2 (g) → CHO(g) + H.sub.2 O.sub.2 (g)              -110     14     28    -105, ΔG.sub.r.sup.0 (298 K.) = +19 kJ                                   mol.sup.-1                                               and                                                                            [I-58]                                                                              HCHO(g) + OH(g) → CHO(g) + H.sub.2 O(g)                            -110     34     28    -229, ΔG.sub.r.sup.0 (298 K.) = -125 kJ                                  mol.sup.-1.                                              ______________________________________                                    

    k([I-55])=3.4×10.sup.-11 exp(-19,600/T)cm.sup.3 molecules.sup.-1 s.sup.-1,                                                 [I-59]

    k(I-56])=3.0×10.sup.-11 exp(-1,500/T)cm.sup.3 molecule.sup.-1 s.sup.-1,                                                 [I-60]

    k([i-57)=3.3×10.sup.-12 exp(-5,870/T)cm.sup.3 molecule.sup.-1 s.sup.-1[I- 61]

and

    k([I-58])=5.7×10.sup.-15 T.sup.1.18 exp(225/T)cm.sup.3 molecule.sup.-1 s.sup.-                                   [I- 62]

    k([I-55], 298K)=9.3×10.sup.-40 cm.sup.3 molecule.sup.-1 s.sup.-1,

    k([I-56], 298K)=1.65×10.sup.-13 cm.sup.3 molecule.sup.-1 s.sup.-1,

    k([I-57], 298K)=9.2×10.sup.-21 cm.sup.3 molecule.sup.-1 s.sup.-1

and

    k([I-58], 298K)=1.01×10.sup.-11 cm.sup.3 molecule.sup.-1 s.sup.-1.

    k([I-55],T)=k(I}-56], 298K).

    3.4×10.sup.-11 exp(-19600/T)=1.65×10.sup.-13

    T=3679 K.

    HCHO(g)=C(graphite)+H.sub.2 (g)+1/2O.sub.2 (g)             [I-63]

and

    K.sub.r ([I-63], 3600K)=1.69.                              [I-64

Again we find that the reactions which are more exo-ergonic are faster. The temperature of 3679K is much too high for an iron reactor. Because formaldehyde is more stabile relative to the elements than methane is, [I-64] is much smaller than [I-51] even though the temperature is much higher.

B. Collision Theory

Although Absolute Reaction Rate Theory, being based on Quantum Mechanics, is more elegant and more definitive than Collision Theory, the latter nonetheless remains quite valuable for the insights which it provides. Unlike Absolute Reaction Rate Theory all reactions, being based on the Kinetic Theory of Gases, Collision Theory is applicable only to gas phase reactions and heterogeneous reactions in which one of the phases is the gas phase.

We begin with the assumption that the gas phase consists of two kinds of molecules, which we designate by A and B, and that the molecules can be approximated by spheres. The diameters of these spheres are d_(A) and d_(B), respectively. If the centers of an A molecule and a B molecule are within a distance

    d.sub.AB =(d.sub.A +d.sub.B)/2,                            [I-65]

collision will occur. The collision frequency will be given by

    Z.sub.AB =πd.sup.2.sub.AB v.sub.AB N.sub.A N.sub.B /V.sup.2, [I-66]

where v_(AB) is the mean relative speed of the two molecules, N_(A) and N_(B) are the number of molecules of A and B, respectively, and V is the volume of the gas phase.

From the Kinetic Molecular Theory of Gases ##EQU14## m_(A) and m_(B) being the masses of molecule A and molecule B, respectively. It should be noted that, although the units of [I-67] appear to be ms⁻¹ (or cm s⁻¹), the units which must be used are actually ms⁻¹ molecule ⁻¹ because v_(A), for example is the sum of the speeds of all of the A molecules divided by the number of A molecules. Most texts ignore this `nicety`. We will find in what follows that our results will have the wrong units if we ignore this `nicety`.

The substitution of [I-67] into [I-66] yields ##EQU15## If A and B are the same kind of molecule, ##EQU16## where the initial factor of 1/2 is to correct for counting each molecule twice--once as a collider and once as a collidee, R is the molar gas constant (8.31 J mol⁻¹ K⁻¹) and M_(A) is the molar mass in kg.

The number of collisions experienced by one molecule in unit time is ##EQU17## and the mean speed is ##EQU18## Thus, the average distance traveled between collisions, the `mean free path`, is ##EQU19##

The triple collision frequency can be estimated by means of the assumption ##EQU20## on the idea that the probability of a third molecule colliding with two molecules which have collided, before they `bounce apart`, is proportional to the ratio of its collision diameter and its mean free path. Thus, ##EQU21##

It will be instructive to evaluate [I-73], [I-70] and [I-75] for some specific cases. At 273K and one atmosphere pressure (STP) 6.02×10²³ molecules occupy ##EQU22##

From <I-2> we obtain the following collision diameters ##EQU23## The average of these three values is 0.294 nm. Thus, we can consider dioxygen to be a `typical` molecule. ##EQU24## It should be noted that J=kgm² s⁻².

If every collision leads to a chemical reaction, the rate constant will be ##EQU25## where the subscript on the k indicates a bimolecular reaction. From <I-3> we obtain the following

    CF.sub.3 (g)+H(g)→CF.sub.2 (g)+HF(g),k.sub.2 =9.1×10.sup.- cm.sup.3 molecule.sup.-1 s.sup.-1,                        [I-80]

    CF.sub.2 (g)+H(g)→CF(g)+HF(g), k.sub.2 =3.9×10.sup.-11 cm.sup.3 molecule.sup.-1 s.sup.-1                         [I- 81]

and

    CF(g)+H(g)→C(g)+HF(g),+HF(g), k.sub.2 =1.9×10.sup.-11 cm.sup.3 molecule.sup.-1 s.sup.-1.                                 [I-82]

Thus, we see that each collision of a monohydrogen and a trifluoromethyl undoubtedly leads to a reaction. It should be noted that, if we had used ms⁻¹, rather than ms.sup.⁻¹ molecule⁻¹, as the units for [I-67], we would not have obtained the correct units for [I-79]. ##EQU26## Thus, for every trimolecular collision at STP about 350 bimolecular collisions occur.

At 0.1 Torr N/V is reduced by a factor of 1/7600 (1 atmosphere=760 Torr). Thus, ##EQU27## Thus, for every trimolecular collision at 273K and 0.1 Torr about 2.6 million bimolecular collisions occur. At 0.1 Torr, therefore, there are effectively no trimolecular collisions, and the mean free path is almost one millimeter!

C. The Arrhenius Equation

No discussion of Chemical Reaction Kinetics would be complete without at least mentioning the Arrhenius Equation.

    k.sub.r =A exp(-E*/kT),                                    [I-87]

an empirical equation which is useful in describing the change in k_(r) with temperature E* is the `activation energy`. A is known as the `frequency factor`, the fraction of the collisions which have the proper orientation of the molecules. A more sophisticated form of [I-87] takes into account that A is actually a function of temperature.

    k.sub.r B(T)exp(`E*/kT).                                   [I-88]

The comparison of [I-88] with [I-35] yields ##EQU28##

If in [I-34] we assume that ΔH.sup. =0 (no enthalpy of activation), ##EQU29## where the factor of V/N is introduced because of the form of the ratio of multiplicities in [I-35]--two molecules combine to form one activated complex,

    (N/V)/(N/V).sup.2 =V/N.

For the formation of a chemical bond the entropy decreases by about 1.7×10⁻²² J bond⁻¹ K⁻¹. In the activated complex about half a bond is formed. Thus, if the molecules do not need a specific orientation to react, ##EQU30## It should be noted that this value is 5.6 times as large as that calculated using `rigid sphere` Collision theory, [I-79].

Referring back to [I-80]-[I-82], we see that the experimental values of the rate constants are all somewhat smaller than that calculated in [I-90]. In the calculation of [I-90] we assumed that `the molecules do not need a specific orientation to react`. Since not all of the surface of CF₃ on collision with H will yield HF, an orientation factor is clearly involved. This is even more so the case with CF₂ and a fortiori the case with CF. Since ##EQU31## this would be the fraction of the surface of the CF molecule which will yield HF on collision with H if CF were a sphere. The area of a portion of a sphere is given by

    A(φ)=2πr.sup.2 (1-COS φ), O≦φ≦180.sup.0.[I-92]

If we equate [I-91] and [I-92] divided by 4πr² (the total surface area of a sphere), we obtain ##EQU32## and

    φ=23.7.sup.o.[I-93]

If we use a circle as the model of CF, then [Io91] is a measure of the fraction of the circumference which is reactive. ##EQU33##

Both of these models are, of course, very poor approximations to the CF molecule, but the fact that I-93] and [I-94] are not that much different is indicative that the value is in the `right ball park`.

IV. THE VFFTE APPARATUS

Before we begin our discussion of the details of the VFFTE chemistries for wafer fabrication, it will be useful to describe the VFFTE apparatus (Apparatus). At this time we will limit our discussion to those aspects of the Apparatus related to wafer-wide chemistries. Those aspects of the apparatus related to patterning will be discussed later.

The Apparatus comprises a vacuum system with a large chamber and a high speed pumping system which will keep most of the chamber at a maximum of 100 nanoTorr. The diameter of the chamber should be at least three times the diameter of the wafer. The chamber is connected to two load locks which can be pumped down independently of the main chamber and each other. The load locks--main chamber complex is equipped with a robotics system which will transfer wafers between the load locks and the main chamber, and which will hold the wafer in place in the main chamber with a minimum of linear and rotational motions during the carrying out of the chemistries.

Above the main chamber and connected to it is the `activation system` which consists of an upper vapor inlet circle, the activation chamber and the lower vapor inlet circle. The activation chamber can be a microwave cavity, a chamber which is irradiated by an electron gun (or guns) providing a defocused beam(s) of high current of low energy (1-25 eV) electrons or a chamber which is irradiated by a tunable laser (or lasers) with a defocused beam(s) with a high flux of photons in the desired energy range.

Since the charge on an electron is 1,602×10⁻¹⁹ C,

    l eV=1.602×10.sup.-19 J.

Furthermore,

    E=hν and c=λν,

therefore ##EQU34## where ν is in wave numbers (cm⁻¹). Thus, ##EQU35##

Into the upper circle is introduced the vapor species which is to be activated. The proper valving and controls are connected to the circle so that several different species are available for activation at controlled flow rates. (Only one species is being activated at a time.) Into the lower circle is introduced the vapor species (or more than one species) which is (are) to react with and/or dilute the activated species. (In some cases no species is introduced into the lower circle. All the chemistries are carried out by the activated species reacting with the materials on the surface of the wafer including, in some cases, the surface of the wafer itself.) As with the upper circle the proper valving and controls are connected to the lower circle so that several different species are available at controlled flow rates.

Since many of the possible species used are toxic, corrosive and/or flammable, the source containers must be enclosed in safety chambers with the appropriate monitor/warning systems in case of leaks. Furthermore, since the effluents may also be toxic, corrosive and/or flammable, the Apparatus must have means for safely disposing of the effluents.

Finally, the apparatus must have a control computer which will control the valves, controls and pumps in the proper sequences as well as the movements of the wafers. The instructions to the control computer can be on tapes or discs or can be inputs from design computers. V. UPPER CIRCLE CHEMISTRIES

A. Introduction

As was indicated in SECTION I. high electric fields near the wafer are to be avoided. This includes the presence of charged particles near or on the surface of the wafer. Thus, activation involving ionization is to be avoided as much as possible. This means that the conditions in the activation chamber should be adjusted to maximize electronic excitation (including dissociation) and minimize ionization. Because the cross section versus energy curves for electronic excitation and ionization frequently peak at widely different energies, these adjustments can be made for the vapor species which we have chosen for discussion here.

Since the excitation-dissociation energies are 3 to 15 eV above the thermodynamic dissociation energies, the particles leaving the activation chamber can have energies 145 to 725 kJ mol⁻¹ above the ground states. The tabulated thermodynamic data are generally for ground states. Thus, reactions may be much more exothermic than the ground state calculations indicate. Furthermore, the excited state species reaction energies may be so great as to cause thermal damage to the wafer. In these cases we dilute and partially de-energize the excited state species by introducing the ground state diatomic species by means of the lower circle. B. Carbon Monoxide

Carbon monoxide is a valuable reagent for the etching of metals which form volatile carbonyls such as Cr(CO)₆ Fe(CO)₆, Mo(CO)₆, Ni(CO)₄ and W(CO)₆. It should be noted that all of these metals have unpaired d-electrons. The ground state of CO is X¹ Σ⁺. Since this state has no unpaired electrons, its rate of reaction with metals at `room temperature` is not very great. The first electronic excited state is a³ π which has two unpaired electrons.

The ionization potential for CO is 14.01 eV <I-4>. The dissociation energy for the X ¹ Σ⁺ state is 11.09 eV <I-5>. The only triplet excited state with a reasonable lifetime is the a³ π state with an excitation energy of 6.01 eV and a lifetime of 7.5-9.5 ms (depending on the vibrational state) <I-6>. By [I-72] ##EQU36## In 9 ms the CO molecule will travel about 1.3 m. Thus, the excited CO molecules will have sufficient time to traverse the distance from the bottom of the activation chamber to the surface of the wafer and react with the metal there.

From cross section curves <I-7> we estimate that the cross section for excitation to the a³ π state at ˜7 eV is ˜1×10⁻¹⁶ cm². The dissociation and ionization cross sections are, of course, zero at ˜7eV.

C. Difluorine

Monofluorine is an extremely powerful oxidizing agent. In addition there are numerous volatile fluorides. The ionization potential of difluorine is 15.7 eV <I-8>, and the dissociation energy is 1.56 eV <I-9>.

Difluorine has a continuous absorption region with a maximum at 2845 Å (4.36 ev) <I-10>. From potential energy curves we estimate the Franck-Condon region excitation energy from the ¹ Σ_(g) ³⁰ ground state to the ¹ .sup.[_(u) repulsive state to be ˜2.7×10⁴ cm⁻¹ (3. 3 eV) to ˜4.2×10⁴ cm⁻¹ (5.2 ev) <I-11>.

D. Dihydrogen

Just as monofluorine is a powerful oxidizing agent, monohydrogen is a powerful reducing agent. In addition there are numerous volatile hydrides. The ionization potential of dihydrogen is 15.4 eV <I-12>. The dissociation energy is 4.48 eV <I-13 >.

Dihydrogen can dissociate to the b³ Σ_(u) ³⁰, H(1s)+H(1s), state or to the B' ¹ Σ_(u) ⁺, H(1s)+H(2s), by excitation from the X ¹ Σ_(g) ⁺ ground state <I-14>. For the excitation to the B' ¹ Σ_(u) ⁺ state

    H.sub.2 (g)+hν→H(1s)+H(2p, 2s),                  [I-98]

    λ=844.7Å(14.68 eV)

<I-13>. Since H (25) and H(2p) have the same energy in the absence of a magnetic field, both products are given. It should be noted that the lifetime of the H(2p) state is only 1.6×10⁻¹⁹ s, whereas the H(2s) state is metastabile with a lifetime of 1.4×10-1 s <I-15>. The peak in the photo dissociation curve is ˜840 Å (14.76V) with a cross section of ˜3.1×10⁻¹⁷ cm² <I-15>. The excitation to the b³ Θ_(u) ⁺ state is reported to have a cross section of ˜9×10⁻¹⁷ cm² at ˜15 eV <I-16>.

Since the transition from the H(2s)/H(2p) states to the H (1s) state is 10.2 eV <I-17>, and since the dissociation energy of dihydrogen is 4.48 eV, the sum is 14.68 eV. Thus, it is possible that the experimental data have been misinterpreted. It may be that the only excitation is that of [I-98]. The apparent dissociation from the b³ Σ_(u) ⁺ state could be the result of the rapid decay of the H(2p) state to the H(1s) state. In any case the required excitation energy for the dissociation of dihydrogen is -14.72-14.8 eV. Since this is so close to the ionization energy of 15.4 eV, the excitation energy must be controlled carefully to avoid the formation of a significant amount of H₂ ⁺.

E. Dioxygen

Monoxygen is a powerful oxidizing agent, but it is not as powerful as monofluorine. There are numerous volatile oxides. The ionization potential of dioxygen is 12.06 eV <I-18>, and the dissociation energy is 5.12 eV <I-19>.

The ground state of dioxygen is the X ³ Σ_(g) ⁻ state. Some of the excited states, their excitation energies <A> and their lifetimes <I-20> are ##EQU37##

Except for the first two excited states all of the excited states are repulsive. The cross section for dissociation is approximately ##EQU38## For ionization plus dissociative ionization Q_(ION) (gross)≈1-2×10⁻¹⁷ cm² <I-21>. The ratio of Q_(DISS) to Q_(ION) (gross) is probably much higher than these numbers would indicate since R. L. McCarthy <I-22> did not find any charged particles outside of the microwave cavity on dissociating dioxygen in a 2.45 GHZ microwave field. Furthermore, he observed a yield of 0.80 gram atoms/kW-hr for monoxygen. ##EQU39## Thus, his system was operating at about 43% efficiency in generating monoxygens if the system was using electrons with an average effective energy of about 20 eV. McCarthy also reported a yield of 1.0 gram atoms of monohydrogen per hW-hr. If the efficiencies are the same for oxygen and hydrogen, the average effective electron energy in the hydrogen case was 16 eV.

E. C. Zipf <I-23> indicates that the excitation energy in the Franck-Condon region of the X 3Σ_(g) ¹ (³ P+³ P) state to the repulsive (³ P+⁵ S) state is around 20 to 27 eV. For 27 eV McCarthy's efficiency is ˜59%. The excitation energy from the monoxygen ground state, ³ P (1s² 2s² 2p⁴) to the ⁵ S^(o) (1s² 2s² 2p³ 2s) state is 9.14 eV <I-24>. With a dissociation energy for dioxygen of 5.12 eV and a ⁵ S excitation energy of 9.14 eV the sum is 14.26 eV. Thus, the monoxygen atoms generated at 20 eV have average kinetic energies of about 2.9 eV. The ⁵ S^(o) state has a lifetime of about 600 μs <I-24>. Substituting 16 for 38 in [I-97] we obtain ##EQU40## In 6×10⁻⁴ S the ⁵ S^(o) atom will have traversed 0.13 m (5.2 inches). Thus, it is likely that very few, if any, ⁵ S atoms will reach the substrate.

In addition to the ⁵ S^(o) excited state there are also the following excited states of monoxygen:

    ______________________________________                                         .sup.1 D    (1s.sup.2 2s.sup.2 2p.sup.4)                                                                    1.96 eV                                           .sup.1 S    (1s.sup.2 2s.sup.2 2.sup.4)                                                                     4.19 eV                                           .sup.3 S.sup.o                                                                             (1s.sup.2 2s.sup.2 2p.sup.3 3s)                                                                 9.52 eV                                           .sup.3 P    (1s.sup.2 2s.sup.2 2p.sup.3 3p)                                                                10.98 eV,                                          ______________________________________                                    

For the dissociation of dioxygen to these excited states the following are reported:

    ______________________________________                                         0(2p.sup.4 .sup.3 P) + 0(3s.sup.1 .sup.3 S.sup.o)                                                     14.65 eV                                                0(2p.sup.4 .sup.3 P) + 0(3p.sup.1 .sup.3 P)                                                           16.12 eV                                                0(2p.sup.4 .sup.1 D) + 0(3s.sup.1 .sup.3 S.sup.o)                                                     16.61 eV                                                0(2p.sup.4 .sup.1 S) + 0(3s.sup.1 .sup.3 S.sup.o)                                                     18.74 eV                                                ______________________________________                                    

<I-25>. Thus, the average kinetic energies of the generated monoxygen atoms may be as low as 0.6 eV. This is, however, still rather high. If a considerable amount of monoxygen is used as in the removal of photoresists, the wafer can absorb a considerable amount of energy. To prevent this undesirable heating of the wafer the monoxygen is diluted with dioxygen from the lower circle. We shall discuss the details of this chemistry later when we discuss photoresist removal.

VFFTE CHEMISTRIES FOR WAFER FABRICATION AND RELATED TECHNOLOGIES PART TWO CLEANING AND ETCHING VI. INTRODUCTION

As was indicated in SECTION III., by means of the lower circle species are introduced which react with and/or dilute the activated species from the upper circle. The discussions following will be concerned with the thermodynamics and kinetics of vapor phase interactions between the upper circle activated species and the lower circle species in a few cases, but mainly they will be concerned with the thermodynamics and kinetics of the heterogeneous reactions of vapor phase species with the surface of the wafer. The thermodynamic data used in the calculations are for the ground state species rather than excited state species. Thus, in most cases the actual reactions are much more energetic than the calculations indicate.

Since the chemistries used for cleaning and etching are the same, the two subjects are discussed together. The topics to be considered are

SECTION VII. REMOVAL OF PARTICULATES

SECTION VIII. REMOVAL OF ORGANICS

SECTION IX. REMOVAL OF INORGANICS.

The analyses of the inorganic substances are organized by the Periodic Table Groups. If the standard state for the element is a condensed phase, it is discussed first. The compounds considered are the oxides, the chlorides, the nitrates and the fluorides--the oxides because of the exposures to monoxygen and dioxygen (e.g. air), the chlorides because of the ubiquitousness of NaCl etc., the nitrates because of the nitric acid etches, and the fluorides because of the hydrofluoric acid etches and the use of monofluorine. In general only those cases are discussed for which there are adequate thermodynamic data.

Frequently, both the vapor phase and one of the condensed phases exist at 298K. An important factor is the equilibrium vapor pressure of the species. This can be calculated by means of the free energy of sublimation or vaporization. Since the standard state of the vapor species is that at one atmosphere pressure, the equilibrium constant is equal to the equilibrium vapor pressure of the vapor phase expressed in atmospheres. Thus, with p as the equilibrium vapor pressure and K as the equilibrium constant

    p=K=exp(-ΔG.sup.0 /298R)

If we require that the vapor pressure be greater than 0.1 Torr, then ##EQU41## If, however, we require that p be greater than 10⁻⁷ Torr, then

    ΔG.sup.0 <56.3 kJ mol.sup.-1 (p>10.sup.-7 Torr).

VII. REMOVAL OF PARTICULATES

It is obvious that as line widths decrease particulate contaminations become a more severe problem. For 10 μm line widths a 0.5 μm diameter particle is not a major cause for concern. For 0.1 μm line widths a 0.5 μm diameter particle can be a disaster. The minimization of the number of particles in the apparatus and the removal of those that are on the wafer's surface is a must. Particulates can `enter` the Apparatus by airborne contamination, by being carried in on the surface of the wafer and by being generated in the apparatus from the rubbing together of moving parts.

Since the main chamber of the Apparatus is entered only by means of the load locks (except during maintenance), since wafers are loaded into, and unloaded from, the locks in stacks rather than individually, and since the locks are pumped down before being opened to the main chamber, the airborne contamination is minimized. Since the wafer is held in place during the carrying out of all the chemistries, the only moving of parts is the opening of the load locks to the main chamber and the moving of the wafer between the load locks and the center of the main chamber, with one wafer being moved to the `unload` lock while another is being moved to the center of the main chamber. Thus, parts are moving only before and after all of the chemistries are carried out. In addition, since the wafers are never touched from the post-polishing cleaning until they are removed from the `unload` lock, the number of particulates on the surface of the wafer is minimized. It is assumed that the post-polishing cleaning is carried out in a simplified version of the Apparatus.

Because maintenance on the Apparatus is a sine qua non, the room in which the Apparatus is located must be a `relatively` clean room. An `ultra-clean` room, however, is not required. Thus, as an additional feature the enormous costs of `ultra-clean` rooms are not required.

Although the species stream approaching the wafer has a pressure of about 0.1 Torr, the majority of the volume of the main chamber is at a maximum of 100 nanoTorr. This large pressure differential generates a force which will `sweep` the particulates off of the surface of the wafer. For the calculations following we shall assume that the particle is iron and is a sphere. The following facts will be used in the calculations: ##EQU42## and

    G=9.81 ms.sup.-2 (the gravitational constant).

Let r be the radius of the particle. The cross sectional area of the particle is

    A=πr.sup.2 (m.sup.2),

and the mass of the particle is ##EQU43## The pressure gradient acting on the particle is ##EQU44## and the force on the particle because of the pressure gradient is ##EQU45## The acceleration of the particle because of F is ##EQU46## For the particle to be moved by the force F, F must be large compared with the gravitational force. Thus, ##EQU47## Thus, we find that the pressure gradient will cause the removal of particulars of the size with which we are concerned provided that the article is not `glued` to the surface by an organic coating or by electrostatic charge. Let us, therefore, now turn to the question of the removal of organics from the surface of the wafer and the surfaces of the particulates. (Since electrostatic charges are found in, or on the surfaces of, insulators, the organic insulators will be removed by the organics removal chemistries. Thus, their electrostatic charges will be removed. Similarly, the inorganic insulators and their electrostatic charges will be removed by the inorganic removal chemistries.)

VIII. REMOVAL OF ORGANICS A. Hydrocarbons

The study of the removal of organics by monoxygen oxidation is complicated by the fact that the monoxygen may be in an excited state and that the products may be in excited states. For the ground state of monoxygen, ³ p (1s² 2s² 2p⁴),

    ΔH.sub.ƒ.sup.0 (O, g, 298K)=249 kJ mol.sup.-1

    ΔG.sub.ƒ.sup.0 (O, g, 298K)=232 kJ mol.sup.-1.

By means of the data in SECTION V.E. we can calculate the heats of formation of some of the excited states of monoxygen:

    ΔH.sub.ƒ.sup.0 (O, .sup.1 D, g, 298K)=438kJ mol.sup.-1

    ΔH.sub.ƒ.sup.0 (O, .sup.1 S, g, 298K)=653kJ mol.sup.-1

    ΔH.sub.ƒ.sup.0 (O, .sup.5 S, g, 298K)=1131kJ mol.sup.-1.

Similarly, the heats of formation of the first two excited states of dioxygen are

    ΔH.sub.ƒ.sup.0 (O.sub.2, .sup.1 Δ.sub.g, g, 298K)=94kJ mol.sup.-1

    ΔH.sub.ƒ.sup.0 (O.sub.2, .sup.1 Σ.sub.g.sup.+, g, 298K)=157kJ mol.sup.-1.

Since the two monoxygens attacking a carbon atom on a surface are coming from the same side of the carbon atom, the electronic state of the carbon dioxide formed may be the A ¹ B₂ (Δ_(u)) state rather than the X ¹ Σ_(g) ⁺ ground state. The ground state is, of course, linear whereas the excited state is bent. The excited state is 8.41 eV above the ground state <II-1>. Thus,

    ΔH.sub.ƒ.sup.0 (CO.sub.2, g, 298K)=-394kJ mol.sup.-1

    ΔG.sub.ƒ.sup.0 (CO.sub.2, g, 298K)=-394kJ mol.sup.-1

    ΔH.sub.ƒ.sup.0 (CO.sub.2, .sup.1 Δ.sub.u, g, 298K)=+418kJ mol.sup.-1

The first excited state of hydroxyl is the A ² Σ³⁰ state which is 4.02 eV above the X ² π_(3/2) ground state <II-2>. Thus,

    ΔH.sub.ƒ.sup.0 (OH, g, 298K)=+.sup.39 kJ mol.sup.-1

    ΔG.sub.ƒ.sup.0 (OH, g, 298K)=+34kJ mol.sup.-1

    i ΔH.sub.ƒ.sup.0 (OH, .sup.2 Σ.sup.30, g, 298K)=+427kJ mol.sup.-1.

In SECTION III.A. we discussed the reaction of methane with monoxygen. We shall continue that discussion here.

    ______________________________________                                         [II-4]                                                                              CH.sub.4 (g) + O(g) → CH.sub.3 (g) + OH(g)                         -75      249    146      39 ΔH.sub.r.sup.0 (298 K.) = +11 kJ                                     mol.sup.-1                                             -51      232    148      34, ΔG.sub.r.sup.0 (298 K.) = +1 kJ                                     mol.sup.-1,                                            k.sub.r (298 K.) = 4.28 × 10.sup.-18 cm.sup.3 molecule.sup.-1            s.sup.-1.                                                                      [II-5]                                                                              CH.sub.4 (g) + O (.sup.1 D, g) → CH.sub.3 (g) + OH(g)              -75      438    146      39, ΔH.sub.r.sup.0 (298 K.) = -178 kJ                                   mol.sup.-1,                                            k.sub.r (298 K.) = 1.4 × 10.sup.-10 cm.sup.3 molecule.sup.-1             s.sup.-1 <II-3>.                                                               [II-6]                                                                              CH.sub.4 (g) + O (.sup.1 S, g) → CH.sub.3 (g) + OH(g)              -75      653    146      39, ΔH.sub.r.sup.0 (298 K.) = -393 kJ                                   mol.sup.-1,                                            [II-7]                                                                              CH.sub.4 (g) + O (.sup.1 S, g) → CH.sub.3 (g) + OH (.sup.2              Σ.sup.+, g)                                                         -75      653    146     427, ΔH.sub.r.sup.0 (298 K.) = -5 kJ                                     mol.sup.-1.                                            ______________________________________                                    

The ⁵ S state of monoxygen, of course, is a much more powerful oxidizing agent than even the ¹ S state of monoxygen. Because of the short lifetime of the ⁵ S state, not many of them can be expected to arrive at the wafer surface.

Of all of the hydrocarbons methane is the most difficult to oxidize. For example, ##STR1## The enthalpies of formation of ethane and ethyl are from <B>, and the rate constant is from >II-4>.

The most difficult step in the oxidation of a hydrocarbon is the abstraction of a hydrogen atom. The formation of the carbon-oxygen bond is much faster. ##STR2##

Even dioxygen is an effective oxidizing agent for the formation of a carbon-oxygen bond. In the following reactions M represents a third body which is required for the removal of the energy of the bond(s) formed. k₂₈ is the second order rate constant under the conditions that the concentration of M is so high that a small change in its concentration has no effect on the rate of the reaction. ##STR3##

The organic molecules discussed above are all small vapor phase species. The organics on the wafer surface, however, are primarily large molecules. Adequate thermodynamic data are not available for most polymers. We shall, therefore, use eicosane, C₂₀ H₄₂, as a model compound. The thermodynamic data for eicosane are

    ΔH.sub.ƒ.sup.0 (g, 298K)=-456kJ mol.sup.-1, <II-7>,

    ΔG.sub.ƒ.sup.0 (g, 298K)=+117kJ mol.sup.-1, <II-7>,

    ΔH.sub.sub (298K)=101kJ mol.sup.-1, <II-8>,

    S.sup.0 (c, 298K)=559J mol.sup.-1 K.sup.-1, <II-9>.

For the solid phase we take ##STR4## Clearly, the monoxygen oxidation of eicosane is highly exothermic and highly exo-ergonic even with the use of ground state monoxygen.

The enormous magnitude of ΔH_(r) ⁰ is however the source of a serious problem. The generation of so much heat will result in the temperature of the wafer being elevated to undesirably high levels. The goal, therefore, is to find a set of conditions for which the ΔH_(r) ⁰ is negative and of sufficient magnitude to ensure a rapid reaction, but not of so large a magnitude as to produce temperature rise problems.

We have noted that the carbon dioxide formed is probably in the ¹ Δ_(u) state. The situation for the excited state of hydroxyl is more complicated and requires some discussion. The ³ p ground state of monoxygen has the electron configuration ##EQU48## The ¹ D excited state has the electron configuration ##STR5## The ¹ S excited state has the electron configuration ##STR6##

The ² π ground state of hydroxyl has two electrons in the σ-bond formed from an oxygen 2p orbital and the hydrogen 1s orbital. Thus, there are a total of three electrons in the other two 2p orbitals. In the ² Σ state the σ-bond has only one electron, and there are a total of four electrons in the other two 2p orbitals of the oxygen. Since the hydrogen is bringing its electron with it to form the σ-bond, the ³ p state of monoxygen can form only the ² π state of hydroxyl. The ¹ D and ¹ S states of monoxygen, on the other hand, can form only the ² Σ state of hydroxyl.

With these facts in mind let us now consider several variations on [II-16]. ##STR7## Thus, we find that by diluting the monoxygen with dioxygen, a small portion of which have been excited by the monoxygen to the ¹ Δ state, we can have the oxidation proceed at a reasonable rate without causing significant heating of the substrate.

If the organic mass is very small, the heat generated is never a problem. When, however, the organic mass is large as is the case with a photoresist layer, the heat generated can be quite large. To analyze the magnitude of the problem let us assume the following:

resist composition--C₂₀ H₄₂ (Molecular Mass 282.6)

resist density--1.0 g cm⁻³

resist thickness--1 μm (10⁻⁴ cm)

wafer diameter--8 inches (20.3 cm).

Eicosane is actually more difficult to oxidize than a polymer. One out of ten of the carbons is a methyl carbon. In polymers this ratio is much lower. The density of eicosane is about 0.8 g cm⁻³, but the density of polymers like the photoresists is about 1.0 g cm⁻³.

The number of `moles` of eicosane in the resist layer is ##EQU49## Using the enthalpy of reaction for [II-19] we calculate the total heat generated to be ##EQU50## The heat capacity of silicon is 20.0 JK¹ mol⁻¹ and the atomic mass is 28.1 g mol⁻¹ <A>. The density of silicon is 2.33 g cm⁻³ <II-10>. Thus, if the wafer is 2.5×10⁻² cm thick and the heat is evenly distributed, the temperature rise is ##EQU51## an insignificant temperature rise.

We must now turn our attention to what could be a much more serious problem. We noted in SECTION V.E. that the two monoxygen atoms formed by the dissociation of dioxygen at 20 eV must have average kinetic energies of about 2.9 eV (2.8×10² kJ mol⁻¹). By [II-20] there are 1.145×10⁻⁴ moles of eicosane, and by [II-19] each mole of eicosane requires 42 gram atoms of monoxygen as well as 20 moles of dioxygen. Thus, the total kinetic energy of the generated monoxygen is ##EQU52## By [II-22] this much energy reaching the wafer, if it were evenly distributed throughout the wafer (which it would not be), would cause a temperature rise of ##EQU53## This much of a temperature rise throughout the wafer would not be serious, but the energy would actually be concentrated at the surface.

The energy required to produce the ¹ Δ dioxygen in ]II-19] is ##EQU54## The kinetic energy of [II-23] is, thus, 62.5 times the amount of energy needed for the ¹ Δ excitation. We must, therefore, find a way to modify the chemistry of [II-19]. One possibility would be to use less monoxygen and more ¹ Δ dioxygen. In the abstraction of a hydrogen atom a dioxygen molecule produces a hydroperoxo (HO₂) rather than the hydroxyl which a monoxygen produces. Thus, if only dioxygens are used, ##STR8## Let us try a `mixture` of [II-19] and [II-26]. ##STR9##

The kinetic energy of the monoxygens in [II-27] is (27/42) times that of [II-23] or 0.87 kJ. The excitation energy necessary to generate the ¹ Δ dioxygens is ##EQU55## Thus, the excess energy is 0.49 kJ. By [II-24] the temperature rise is ##EQU56## For [II-27] the ratio of dioxygen entering the lower circle to that entering the upper circle is 35:(27/2)=2.6. Thus, with a ratio of the order of 3:1 the removal of the photoresist can be carried out at a reasonable rate without significant heating of the wafer. The exact value of the ratio has to be determined experimentally since all photoresists are not alike, every monoxygen generated will not reach the wafer (some will diffuse out of the `target` area) and not all collisions between monoxygens and dioxygens will result in the excitation of the dioxygen to the ¹ Δ state.

B. Fluorocarbons

Fluorocarbons play a key role in the deposition of low dielectric constant dielectrics. The vaporization reagent of choice here is monohydrogen. As a demonstration of the efficacy of monohydrogen in the breaking of carbon-fluorine bonds we consider the stepwise reactions of tetrafluoromethane with monohydrogen.

    ______________________________________                                         [II-28]                                                                              CF.sub.4 (g) + H(g) → CF.sub.3 (g) + HF(g)                        -933       218     -470      -272, ΔH.sub.r.sup.0 (298 K.) =                                          -27 kJ mol.sup.-1                                 -888       203     -457      -275, ΔG.sub.r.sup.0 (298 K.) =                                          -47 kJ mol.sup.-1,                                [II-29]                                                                              CF.sub.3 (g) + H(g) → CF.sub.2 (g) + HF(g)                        -470       218     -182      -272, ΔH.sub.r.sup.0 (298 K.) =                                          -202 kJ mol.sup.-1                                -457       203     -192      -275, ΔG.sub.r.sup.0 (298 K.) =                                          -213 kJ mol.sup.-1,                               [II-30]                                                                              CF.sub.2 (g) + H(g) → CF(g) + HF(g)                               -182       218      255      -272, ΔH.sub.r.sup.0 (298 K.) =                                          -53 kJ mol.sup.-1                                 -192       203      224      -275, ΔG.sub.r.sup.0 (298 K.) =                                          -62 kJ mol.sup.-1                                 and                                                                            [II-31]                                                                              CF(g) + H(g) → C(g) + HF(g)                                        255       218      717      -272, ΔH.sub.r.sup.0 (298 K.) =                                          -28 kJ mol.sup.-1                                  224       203      671      -275, ΔG.sub.r.sup.0 (298 K.) =                                          -31 kJ mol.sup.-1.                                ______________________________________                                    

Based on the thermodynamic data the expectation is that [II-28]-[II-31] are fast reactions. This expectation is substantiated by the experimental data. The rate constants for [II-29]-[II-31] are 9×10⁻¹¹, 3.9×10⁻¹¹ and 1.9×10⁻¹¹ cm³ molecule⁻¹ s⁻¹, respectively (cf. [II-80]-[II-82]).

Having demonstrated the efficiency of monohydrogen in breaking carbon-fluorine bonds, we must now consider the efficacy of monohydrogen in breaking carbon-carbon bonds in fluorocarbons.

    ______________________________________                                         [II-32]                                                                              C.sub.2 F.sub.6 (g) + H(g) → CF.sub.3 H(g) + CF.sub.3 (g)         -1344      218     -697      -470, ΔH.sub.r.sup.0 (298 K.) =                                          -41 kJ mol.sup.-1                                 -1258      203     -663      -457, ΔG.sub.r.sup.0 (298 K.) =                                          -65 kJ mol.sup.-1.                                ______________________________________                                    

Finally, we consider the volatilization of polytetrafluoroethylene by monohydrogen.

    __________________________________________________________________________     [II-32]                                                                            l/n (C.sub.2 F.sub.4).sub.n (cr) + 12 H(g) → 2CH.sub.4 (g) +            4HF(g)                                                                     -820    12 × 218                                                                      2 × -75                                                                       4 × -272, ΔH.sub.r.sup.0 (298 K.) = -3034                          kJ mol.sup.-1.                                               __________________________________________________________________________

The datum on polytetrafluoroethylene is from <B>.

IX. REMOVAL OF INORGANICS A. General Principles

In SECTION V.E. we noted that the dioxygen at 20 eV must have average kinetic energies of about 2.9 eV (280 kJ mol⁻¹). Similarly, in SECTION V.C. we noted that the dissociation of difluorine to two monofluorines is 1.56 eV, but that the Franck-Condon region excitation energy is 3.3 eV to 5.2 eV. If we assume that the excitation energy is 5.0 eV, the average kinetic energy of the monofluorines formed is ##EQU57##

In considering monoxygen or monofluorine as volatilizing reagents these kinetic energies must be added to the enthalpies of formation to obtain the enthalpies of reaction for reactions in which these species are reagents. Not all of the enthalpy of reaction, however, will go into volatilizing the oxides or fluorides formed. Some will go into the kinetic energies of the volatile species, and some will go into the heating of the substrate. In our analyses we shall assume that the enthalpy of reaction must be at least four times that of the enthalpy of sublimation of the oxide or fluoride. The enthalpies of reaction calculated using the ground state enthalpies of all species will be designated in the usual way by ΔH_(r) ⁰ (298K). The enthalpies of reaction calculated using the excited state enthalpy for at least one species will be designated ΔH_(r) ^(o) (298K).

B. Group IA.

1. THERMODYNAMIC DATA

We note that none of the condensed phase compounds listed in TABLE II-1 are self-volatilizing under the criteria of [II-1] or [II-2].

2. LITHIUM

The enthalpies of sublimation of the oxides and fluoride of lithium are

    ______________________________________                                         Li.sub.2 O    432 kJ mol.sup.-1                                                                             (1728)                                            Li.sub.2 O.sub.2                                                                             390 kJ mol.sup.-1                                                                             (1560)                                            LiF           270 kJ mol.sup.-1                                                                             (1080).                                           ______________________________________                                    

The numbers in the parentheses are the `times four` values.

    ______________________________________                                         [II-34]                                                                              2Li(cr) = O(g) → Li.sub.2 O(cr)                                   2 × 0                                                                              249    -599,   ΔH.sub.r.sup.0 (298 K.) = -848 kJ                                        mol.sup.-1                                                                     ΔH.sub.r.sup.0 (298 K.) = -1128 kJ                                       mol.sup.-1,                                           2 × 0                                                                              232    -562,   ΔH.sub.r.sup.0 (298 K.) = -794 kJ                                        mol.sup.-1,                                           ______________________________________                                    

                                      TABLE II-1                                   __________________________________________________________________________     GROUP IA                                                                       THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES                                                                              Li      Na      K       Rb      Cs                                       __________________________________________________________________________     M.sub.2 O                                                                      (cr)  -599/-562                                                                               418/-379                                                                              -363/-322                                                                              -339*/--                                                                                346/-308                                (g)   -167/-187                                                                              -36*/-52*                                                                              -63*/-- -50*/--  -92/-106                                M.sub.2 O.sub.2                                                                (cr)  -633/-571                                                                              -513/-450                                                                              -496/-430                                                                              -472*/--                                                                               --                                       (g)   -243/-246                                                                              --      -159*/--                                                                               --      -247*/--                                 MO    +84/+60 +84/+61 +71/+50 --      +63/+43                                  (g)                                                                            MCl                                                                            (cr)  -408/-384                                                                              -411/-384                                                                              -437/-409                                                                              -435*/-408*                                                                            -443/-414                                (g)   -196/-217                                                                              -181/-201                                                                              -215/-233                                                                              -229*/-247*                                                                            -240/-258                                MF                                                                             (cr)  -611/-589                                                                              -575/-545                                                                              -569/-539                                                                              -558*/--                                                                               -555/-525                                (g)   -341/-362                                                                              -290/-310                                                                              -327/-345                                                                              -331*/-349*                                                                            -356/-372                                MNO.sub.3                                                                            -483*/-381                                                                             -468*/-367*                                                                            -495*/-395*                                                                            -495*/-396*                                                                            -506*/-407*                              (cr)                                                                           __________________________________________________________________________      (*Ref. <B>).                                                             

    __________________________________________________________________________     [ II-35]                                                                           Li.sub.2 O(cr) + O(g) → Li.sub.2 O.sub.2 (cr)                       -599    249                                                                               -633,                                                                              ΔH.sub.r.sup.0 (298 K.) = -283 kJ mol.sup.-1                             ΔH.sub.r.sup.0 (298 K.) = -563 kJ mol.sup.-1              -562    232                                                                               -571,                                                                              ΔG.sub.r.sup.0 (298 K.) = -241 kJ mol.sup.-1,             [II-36]                                                                            2 LiCl(cr) = 3 O(g) → Li.sub.2 O(cr) + 2 ClO(g)                     2 × -408                                                                           3 × 249                                                                       -599                                                                               2 × 101,                                                                       ΔH.sub.r.sup.0 (298 K.) = -328 kJ                                        mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -1222 kJ mol.sup.-1        2 × -384                                                                           3 × 232                                                                       -562                                                                               2 × 98,                                                                        ΔG.sub.r.sup.0 (298 K.) = -294 kJ                                        mol.sup.-1,                                           [II-37]                                                                            2 LiCl(cr) + 6 O(g) → Li.sub.2 O.sub.2 (cr) + 2ClO.sub.2 (g)        2 × -408                                                                           6 × 249                                                                       -633                                                                               2 × 102*,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1107 kJ                                       mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2787 kJ mol.sup.-1        2 × -384                                                                           6 × 232                                                                       -571                                                                               2 × 120*,                                                                      ΔG.sub.r.sup.0 (298 K.) = -955 kJ                                        mol.sup.-1                                            [II-38]                                                                            2 LiF(cr) + 3 O(g) → Li.sub.2 O(cr) = 2 FO(g)                       2 × -617                                                                           3 × 249                                                                       -599                                                                               2 × 109,                                                                       ΔH.sub.r.sup.0 (298 K.) = +106 kJ                                        mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -734 kJ mol.sup.-1         2 × -589                                                                           3 × 232                                                                       -562                                                                               2 × 105,                                                                       ΔG.sub.r.sup.0 (298 K.) = +130 kJ                                        mol.sup.-1                                            and                                                                            [II-39]                                                                            2 LiF(cr) = 6 O(g) →  Li.sub.2 O.sub.2 (cr) + 2 FO.sub.2 (g)        2 × -617                                                                           6 × 249                                                                       -633                                                                               2 × 13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -867 kJ                                        mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2547 kJ mol.sup.-1        2 × -589                                                                           6 × 232                                                                       -571                                                                               2 × 27,                                                                        ΔG.sub.r.sup.0 (298 K.) = -745 kJ                                        mol.sup.-1.                                           __________________________________________________________________________      (*Ref. <B>).                                                             

Although [II-37] and [II-39] are sufficiently energetic that some lithium peroxide may volatilize, even excess monoxygen reacting with lithium oxide will not generate sufficient energy to volatilize the lithium peroxide formed. Thus, the monoxygen used to remove organics will not by itself also remove all the lithium species.

    __________________________________________________________________________     [II-40]                                                                            Li.sub.2 O(cr) + 4 F(g) → 2 LiF(cr) + F.sub.2 O(g)                  -599    4 × 79                                                                        2 × -617                                                                       24,  ΔH.sub.r.sup.0 (298 K.) = 927 kJ                                         mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -1591 kJ mol.sup.-1         -562    4 × 62                                                                        2 × -587                                                                       42,  ΔG.sub.r.sup.0 (298 K.) = -822 kJ                                        mol.sup.-1,                                            [II-41]                                                                            Li.sub.2 O.sub.2 (cr) + 6 F(g) → 2 LiF(cr) + 2 F.sub.2 O(g)         -633    6 × 79                                                                        2 × -617                                                                       2 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1027 kJ                                       mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2023 kJ mol.sup.-1         -571    6 × 62                                                                        2 × -587                                                                       2 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -895 kJ mol.sup.                               -1                                                     and                                                                            [II-42]                                                                            LiNO.sub.3 (cr) + 10 F(g) → LiF(cr) + NF.sub.3 (g) + 3 F.sub.2          O(g)                                                                       -483    10 × 79                                                                       -617                                                                               -124                                                                               3 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -976 kJ                                        mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2636 kJ mol.sup.-1       -381    10 × 62                                                                       -587                                                                               -83 3 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -783 kJ                                        mol.sup.-1.                                          __________________________________________________________________________

Of the three reactions with monofluorine only, [II-42] is sufficiently energetic to meet the `times four` criterion. This suggests that it is advisable to add nitrogen dioxide to the dioxygen in the lower circle. Thus,

    __________________________________________________________________________     [II-43]                                                                            Li.sub.2 O(cr) + O(g) + 2NO.sub.2 (g) → 2 LiNO.sub.3 (cr)           -599    249  2 × 33                                                                        2 × -483, ΔH.sub.r.sup.0 (298 K.) = -682 kJ                        mol.sup.-1                                                   -562    232  2 × 51                                                                        2 × -381, ΔG.sub.r.sup.0 (298 K.) = -534 kJ                        mol.sup.-1,                                                  and                                                                            [II-44]                                                                            Li.sub.2 O.sub.2 (cr) + 2 NO.sub.2 (g) → 2 LiNO.sub.3 (cr)          -633    2 × 33                                                                        2 × -483, ΔH.sub.r.sup.0 (298 K.) = -399 kJ                        mol.sup.-1                                                        -571    2 × 51                                                                        2 × -381, ΔG.sub.r.sup.0 (298 K.) = -293 kJ                        mol.sup.-1.                                                       __________________________________________________________________________

By this means we can convert all of the lithium compounds to lithium nitrate during the monoxygen reactions. Dioxygen, of course, is used in the lower circle only when there is a large quantity of organics to remove. When this is not the case only nitrogen dioxide need be used in the lower circle. In our analyses of the chemistries of the other alkali metals we shall consider the conversion of all compounds to the nitrates during the monoxygen reactions.

3. SODIUM

The enthalpy of sublimation of sodium fluoride is 285 kJ mol⁻¹. The `times four` criterion is, therefore, 1140 kJ mol⁻¹.

    __________________________________________________________________________     [II-45]                                                                            Na(cr) + O(g) + NO.sub.2 (g) → NaNO.sub.3 (cr)                      0       249  33  -468, ΔH.sub.r.sup.0 (298 K.) = -750 kJ                                        mol.sup.-1                                              0       232  51  -369, ΔG.sub.r.sup.0 (298 K.) = -652 kJ                                        mol.sup.-1,                                             [II-45]                                                                            Na.sub.2 O(cr) + O(g) + 2 NO.sub.2 (g) → 2 NaNO.sub.3 (cr)          -418    249  2 × 33                                                                       2 × -468,                                                                      ΔH.sub.r.sup.0 (298 K.) = -833 kJ                                        mol.sup.-1                                              -379    232  2 × 51                                                                       2 × -369,                                                                      ΔG.sub.r.sup.0 (298 K.) = -693 kJ                                        mol.sup.-1,                                             [II-46]                                                                            Na.sub.2 O.sub.2 (cr) + 2 NO.sub.2 (g) → 2 NaNO.sub.3 (cr)          -513    2 × 33                                                                        2 × -468, ΔH.sub.r.sup.0 (298 K.) = -489 kJ                        mol.sup.-1                                                        -450    2 × 51                                                                        2 × -369, ΔG.sub.r.sup.0 (298 K.) = -390 kJ                        mol.sup.-1,                                                       [II-47]                                                                            NaCl(cr) + 3 O(g) + NO.sub.2 (g) → NaNO.sub.3 (cr) + ClO.sub.2          (g)                                                                        -411    3 × 249                                                                       33  -468                                                                               102, ΔH.sub.r.sup.0 (298 K.) = -735 kJ                                        mol.sup.-1                                           -384    3 × 232                                                                       51  -369                                                                               120, ΔG.sub.r.sup.0 (298 K.) = -612 kJ                                        mol.sup.-1,                                          [II-48]                                                                            NaF(cr) + 3 O(g) + NO.sub.2 (g) → NaNO.sub.3 (cr) + FO.sub.2            (g)                                                                        -575    3 × 249                                                                       33  -468                                                                               13,  ΔH.sub.r.sup.0 (298 K.) = -660 kJ                                        mol.sup.-1                                           -545    3 × 232                                                                       51  -369                                                                               27,  ΔG.sub.r.sup.0 (298 K.) = -544 kJ                                        mol.sup.-1                                           and                                                                            [II-49]                                                                            NaNO.sub.3 (cr) + 10F(g) → NaF(cr) +  NF.sub.3 (g) + 3F.sub.2           O(g)                                                                       -468    10 × 79                                                                       -575                                                                               -124                                                                               3 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -949 kJ                                        mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2609 kJ mol.sup.-1       -369    10 × 62                                                                       -545                                                                               -83 3 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -753 kJ                                        mol.sup.-1.                                          __________________________________________________________________________

The `times four` criterion of 1140 kJ mol⁻¹ is easily met. Thus, the O/NO₂ +F procedure works well for the removal of all sodium species.

4. POTASSIUM

The enthalpy of sublimation of potassium fluoride is 242 kJ mol⁻¹. The `times four` criterion is, thus, 968 kJ mol⁻¹.

    __________________________________________________________________________     [II-50]                                                                            K(cr) + O(g) + NO.sub.2 (g) → KNO.sub.3 (cr)                        0       249                                                                               33  -495, ΔH.sub.r.sup.0 (298 K.) = -777 kJ mol.sup.-1        0       232                                                                               51  -395, ΔH.sub.r *(298 K.) = -678 kJ mol.sup.-1,            [II-51]                                                                            K.sub.2 O(cr) + O(g) + 2 NO.sub.2 (g) → 2 KNO.sub.3                 -363    249                                                                               2 × 33                                                                       2 × -495,                                                                      ΔH.sub.r.sup.0 (298 K.) = -942 kJ mol.sup.-1        -322    232                                                                               2 × 51                                                                       2 × -395,                                                                      ΔG.sub.r.sup.0 (298 K.) = -802 kJ mol.sup.-1,       [II-52]                                                                            K.sub.2 O.sub.2 (cr) + 2 NO.sub.2 (g) → 2 KNO.sub.3                 -496    2 × 33                                                                       2 × -495,                                                                      ΔH.sub.r.sup.0 (298 K.) = -560 kJ mol.sup.-1           -430    2 ×  51                                                                      2 × -395,                                                                      ΔG.sub.r.sup.0 (298 K.) = -462 kJ mol.sup.-1,          [II-53]                                                                            KCl(cr) + 3O(g) + NO.sub.2 (g) → KNO.sub.3 (cr) + ClO.sub.2             (g)                                                                        -437    3 × 249                                                                       33  -495                                                                               102,                                                                               ΔH.sub.r.sup.0 (298 K.) = -736 kJ                                        mol.sup.-1                                            -409    3 × 232                                                                       51  -395                                                                               120,                                                                               ΔG.sub.r.sup.0 (298 K.) = -613 kJ                                        mol.sup.-1,                                           [II-54]                                                                            KF(cr) + 3O(g) + NO.sub.2 (g) → KNO.sub.3 (cr) + FO.sub.2 (g)       -569    3 × 249                                                                       33  -495                                                                               13, ΔH.sub.r.sup.0 (298 K.) = -693 kJ                                        mol.sup.-1                                            -539    3 × 232                                                                       51  -395                                                                               27, ΔG.sub.r.sup.0 (298 K.) = -576 kJ                                        mol.sup.-1,                                           and                                                                            [II-55]                                                                            KNO.sub.3 (cr) × 10F(g) → KF(cr) + NF.sub.3 (g) + 3               F.sub.2 O(g)                                                               -495    10 × 79                                                                       -569                                                                               -124                                                                               3 × 24,                                                                      ΔH.sub.r.sup.0 (298 K.) = -916 kJ                                        mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2576 kJ mol.sup.-1        -395    10 × 6                                                                        -539                                                                               -83 3 × 42,                                                                      ΔH.sub.r.sup.0 (298 K.) = -721 kJ                                        mol.sup.-1.                                           __________________________________________________________________________

The `times four` criterion of 968 kJ mol⁻¹ is easily met. Thus, the O/NO₂ +F procedure works well for the removal of all potassium species.

5. RUBIDIUM

The enthalpy of sublimation of rubidium fluoride is 227 kJ mol⁻¹. The `times four ` criterion is, therefore, 908 kJ mol⁻¹.

    __________________________________________________________________________     [II-56]                                                                            Rb(cr) + O(g) + NO.sub.2 (g) → RbNO.sub.3 (cr)                      0       249                                                                               33  -495, ΔH.sub.r.sup.0 (298 K.) = -777 kJ mol.sup.-1        0       232                                                                               51  -396, ΔG.sub.r.sup.0 (298 K.) = -679 kJ mol.sup.-1,       [II-57]                                                                            Rb.sub.2 O(cr) + O(g) + 2 NO.sub.2 (g) → 2 RbNO.sub.3 (cr)          -339    249                                                                               2 × 33                                                                       2 × -495,                                                                      ΔH.sub.r.sup.0 (298) = -966 kJ mol.sup.-1,          [II-58]                                                                            Rb.sub.2 O.sub.2 (cr) + 2NO.sub.2 (g) → 2 RbNO.sub.3 (cr)           -472    2 × 33                                                                       2 × -495,                                                                    ΔH.sub.r.sup.0 (298 K.) = -584 kJ mol.sup.-1,            [II-59]                                                                            RbCl(cr) + 3O(g) + NO.sub.2 (g) → RbNO.sub.3 (cr) + ClO.sub.2           (g)                                                                        -435    3 × 249                                                                       33  -495                                                                               102,                                                                               ΔH.sub.r.sup.0 (298 K.) = -738 kJ                                        mol.sup.-1                                            -408    3 × 232                                                                       51  -396                                                                               120,                                                                               ΔG.sub.r.sup.0 (298 K.) = -615 kJ                                        mol.sup.-1,                                           [II-60]                                                                            RbF(cr) + 3O(g) + NO.sub.2 (g) → RbNO.sub.3 (cr) + FO.sub.2             (g)                                                                        -558    3 × 249                                                                       33  -495                                                                               13, ΔH.sub.r.sup.0 (298 K.) = -704 kJ                                        mol.sup.-1                                            and                                                                            [II-61]                                                                            RbNO.sub.3 (cr) + 10F(g) → RbF(cr) + NF.sub.3 (g) + 3F.sub.2            O(g)                                                                       -495    10 × 79                                                                       -558                                                                               -124                                                                               3 × 24,                                                                      ΔH.sub.r.sup.0 (298 K.) = -905 kJ                                        mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2565 kJ                   __________________________________________________________________________                              mol.sup.-1.                                      

The `times four` criterion of 908 kJ mol⁻¹ is easily met, and the O/NO₂ +F procedure works well for the removal of all rubidium species.

6. CESIUM

The enthalpy of sublimation of cesium fluoride is 199 kJ mol⁻¹, and the `times four` criterion is 796 kJ mol⁻¹.

    __________________________________________________________________________     [II-62]                                                                            Cs(cr) + O(g) + NO.sub.2 (g) → CsNO.sub.3 (cr)                      0       249  33  -506,    ΔH.sub.r.sup.0 (298 K.) = -788 kJ                                        mol.sup.-1                                           0       232  51  -407,    ΔG.sub.r.sup.0 (298 K.) = -690 kJ                                        mol.sup.-1,                                          [II-63]                                                                            Cs.sub.2 O(cr) + O(g) + 2NO.sub.2 (g) → 2 CsNO.sub.3 (cr)           346     249  2 × 33                                                                       2 × -506,                                                                         ΔH.sub.r.sup.0 (298 K.) = -981 kJ                                        mol.sup.-1                                           -308    232  2 × 51                                                                       2 × -407,                                                                         ΔG.sub.r.sup.0 (298 K.) = -840 kJ                                        mol.sup.-1,                                          [II-64]                                                                            CsCl(cr) + 3O(g) + NO.sub.2 (g) → CsNO.sub.3 (cr) + ClO.sub.2           (g)                                                                        -443    3 × 249                                                                       33  -506                                                                               102, ΔH.sub.r.sup.0 (298 K.) = -741 kJ                                        mol.sup.-1                                           -414    3 × 232                                                                       51  -407                                                                               120, ΔG.sub.r.sup.0 (298 K.) = -620 kJ                                        mol.sup.-1,                                          [II-65]                                                                            CsF(cr) + 3O(g) + NO.sub.2 (g) → CsNO.sub.3 (cr) + FO.sub.2             (g)                                                                        -555    3 × 249                                                                       33  -506                                                                               13,  ΔH.sub.r.sup.0 (298 K.) = -718 kJ                                        mol.sup.-1                                           -525    3 × 232                                                                       51  -407                                                                               27,  ΔG.sub.r.sup.0 (298 K) = -602 kJ                                         mol.sup.-1                                           and                                                                            [II-66]                                                                            CsNO.sub.3 (cr) + 10F(g) → CsF(cr) + NF.sub.3 (g) + 3F.sub.2            O(g)                                                                       -506    10 × 79                                                                       -555                                                                               -124                                                                               3 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -891 kJ                                        mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2551 kJ mol.sup.-1       -407    10 × 62                                                                       -525                                                                               -83 3 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = - 695 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

The `times four` criterion is met for [II-66] even without considering the kinetic energy of the monofluorines. The O/NO₂ +F procedure works well for the removal of all cesium species.

C. Group IIA.

1. THERMODYNAMIC DATA

                                      TABLE II-2                                   __________________________________________________________________________     GROUP IIA                                                                      THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES Be      Mg      Ca      Sr      Ba                                     __________________________________________________________________________     Mo   (cr)                                                                              -608/-579                                                                              -601/-569                                                                              -635/-604                                                                              -592/-561                                                                             -548/-520                                    (g)                                                                               +136/+111                                                                              +58/+35 +44/+21 -13/-35                                                                               -124/-145                               MCl.sub.2                                                                           (cr)                                                                              -491/-466                                                                              -642/-592                                                                              -796/-748                                                                              -829/-780                                                                             -859/-810                                    (g)                                                                               -360/-366                                                                              -392/-399                                                                              -472/-479                                                                              -473/-484                                                                             -499/-511                               MF.sub.2                                                                            (cr)                                                                              -1027/-979                                                                             -1124/-1071                                                                            -1226/-1173                                                                            -1217/-1165                                                                           -1209/-1158                                  (g)                                                                               -796/-801                                                                              -727/-733                                                                              -789/-793                                                                              -766/776                                                                              -804/-814                               M(NO.sub.3).sub.2                                                                   (cr)                                                                              --      -791*/-589*                                                                            -938*/-743*                                                                            -978*/780*                                                                            -992*/797*                              __________________________________________________________________________      (*Ref. <B>).                                                             

We note that none of the condensed phase compounds listed in TABLE II-2. are self-volatilizing under the criteria of [II-1] or [II-2].

2. BERYLLIUM

The enthalpy of sublimation of beryllium fluoride is 231 kJ mol⁻¹. The `times four` criterion is 924 kJ [mol⁻¹. In the absence of any thermodynamic data on beryllium nitrate we are unable to investigate the reactions of nitrogen dioxide with compounds of beryllium.

    __________________________________________________________________________     [II-67]                                                                            Be(cr) + O(g) → BeO(cr)                                             0       249  -608,    ΔH.sub.r.sup.0 (298 K.) = -857 kJ mol.sup.-1       0       232  -579,    ΔG.sub.r.sup.0 (298 K.) = -811 kJ                                        mol.sup.-1,                                              [II-68]                                                                            BeCl.sub.2 (cr) + 5O(g) → BeO(cr) + 2ClO.sub.2 (g)                  -491    5 × 249                                                                       -608                                                                               2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1158 kJ                                       mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -2558 kJ mol.sup.-1           -466    5 × 232                                                                       -579                                                                               2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1033 kJ                                       mol.sup.-1,                                              [II-69]                                                                            BeF.sub.2 (cr) + 5O(g) → BeO(cr) + 2FO.sub.2 (g)                    -1027   5 × 249                                                                       -608                                                                               2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -800 kJ mol.sup.-1                             ΔH.sub.r *(298 K.) = -2200 kJ mol.sup.-1           -979    5 × 232                                                                       -579                                                                               2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -706 kJ mol.sup.-1       and                                                                            [II-70]                                                                            BeO(cr) + 4F(g) → BeF.sub.2 (cr) + F.sub.2 O(g)                     -608    4 × 79                                                                        -1027                                                                              24,  ΔH.sub.r.sup.0 (298 K.) = -711 kJ mol.sup.-1                             ΔH.sub.r *(298) = -1375 kJ mol.sup.-1              -579    4 × 62                                                                        -979                                                                               42,  ΔG.sub.r.sup.0 (298 K.) = -606 kJ                  __________________________________________________________________________                           mol.sup.-1.                                         

Thus, [II-70] exceeds the `times four` criterion for beryllium fluoride. The `times four` criterion for BeO is 2976 kJ mol⁻¹ which neither [II-68] or [II-69] meet. Thus, the O+F procedure works well for the removal of all species of beryllium considered even in the absence of NO₂.

3. MAGNESIUM

The enthalpy of sublimation of magnesium fluoride is 397 kJ mol⁻¹, and the `times four` criterion is 1588 kJ mol⁻¹.

    __________________________________________________________________________     [II-71]                                                                            Mg(cr) + 2O(g) + 2NO.sub.2 (g) → Mg(NO.sub.3).sub.2                 0       2 × 249                                                                       2 × 33                                                                       -791,      ΔH.sub.r.sup.0 (298 K.) = -1355 kJ                                       mol.sup.-1                                         0       2 × 232                                                                       2 × 51                                                                       -589,      ΔG.sub.r.sup.0 (298 K.) = -1155 kJ                                       mol.sup.-1,                                        [Ii-72]                                                                            MgO(cr) + O(g) + 2NO.sub.2 (g) → Mg(NO.sub.3).sub.2                 -601    249  2 × 33                                                                       -791,      ΔH.sub.r.sup.0 (298 K.) = -505 kJ                                        mol.sup.-1                                         -569    232  2 × 51                                                                       -589,      ΔG.sub.r.sup.0 (298 K.) = -354 kJ                                        mol.sup.-1,                                        [II-73]                                                                            MgCl.sub.2 (cr) + 6O(g) + 2NO.sub.2 (g) → Mg(NO.sub.3).sub.2 +          2ClO.sub.2 (g)                                                             -642    6 × 249                                                                       2 × 33                                                                       -791  2 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1505 kJ                                      mol.sup.-1                                         -592    6 × 232                                                                       2 × 51                                                                       -589  2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1251 kJ                                       mol.sup.-1,                                        [II-74]                                                                            MgF.sub.2 (cr) + 6O(g) + 2NO.sub.2 (g) → Mg(NO.sub.3).sub.2 +           2FO.sub.2 (g)                                                              -1124   6 × 249                                                                       2 × 33                                                                       -791  2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1201 kJ                                       mol.sup.-1                                         -1071   6 × 232                                                                       2 × 51                                                                       -589  2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -958 kJ                                        mol.sup.-1                                         and                                                                            [II-75]                                                                            Mg(NO.sub.3).sub.2 (cr) + 20F(g) → MgF.sub.2 (cr) + 2NF.sub.3           (g) + 6F.sub.2 O(g)                                                        -791    20 × 79                                                                       -1124                                                                              2 × -124                                                                       6 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) =  -2017 kJ                                      mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -5337 kJ                                            mol.sup.-1                                         -589    20 × 62                                                                       -1071                                                                              2 × -83                                                                        6 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1636 kJ                                       mol.sup.-1.                                        __________________________________________________________________________

The `times four` criterion is met for [II-75] even without considering the kinetic energy of the monofluorines. Thus, the O/NO₂ +F procedure works well for the removal of all magnesium species.

4. CALCIUM

The enthalpy of sublimation of calcium fluoride is 442 kJ mol⁻¹, and the `times four` criterion is 1768 kJ mol⁻¹.

    __________________________________________________________________________     [II-76]                                                                            Ca(cr) + 2O(g) + 2NO.sub.2 (g) → Ca(NO.sub.3).sub.2 (cr)            0       2 × 249                                                                       2 × 33                                                                        -938,      ΔH.sub.r.sup.0 (298 K.) = -1436 kJ                                       mol.sup.-1                                        0       2 × 232                                                                       2 × 51                                                                        -743,      ΔG.sub.r.sup.0 (298 K.) = -1207 kJ                                       mol.sup.-1,                                       [II-77]                                                                            CaO(cr) + O(g) + 2NO.sub.2 (g) → Ca(NO.sub.3).sub.2 (cr)            -635    249  2 × 33                                                                        -938,      ΔH.sub.r.sup.0 (298 K.) = -kJ                                            mol.sup.-1                                        -604    232  2 × 51                                                                        -743,      ΔG.sub.r.sup.0 (298 K.) = -473 kJ                                        mol.sup.-1,                                       [II-78]                                                                            CaCl.sub.2 (cr) + 6O(g) + 2NO.sub.2 (g) → Ca(NO.sub.3).sub.2            (cr) + 2ClO.sub.2 (g)                                                      -796    6 × 249                                                                       2 × 33                                                                        -938  2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1498 kJ                                       mol.sup.-1                                        -748    6 × 232                                                                       2 × 51                                                                        -743  2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1249 kJ                                       mol.sup.-1,                                       [II-79]                                                                            CaF.sub.2 (cr) + 6O(g) + 2NO.sub.2 (g) → Ca(NO.sub.3).sub.2             (cr) + 2FO.sub.2 (g)                                                       -1226   6 × 249                                                                       2 × 33                                                                        -938  2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1246 kJ                                       mol.sup.-1                                        -1173   6 × 232                                                                       2 × 51                                                                        -743  2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1010 kJ                                       mol.sup.-1                                        and                                                                            [II-80]                                                                            Ca(NO.sub.3).sub.2 (cr) + 20F(g) → CaF.sub.2 (cr) + 2NF.sub.3           (g) + 6F.sub.2 O(g)                                                        -938    20 × 79                                                                       -1226                                                                               2 × -124                                                                       6 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) =  -1972 kJ                                      mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -5292 kJ                                            mol.sup.-1                                        -743    20 × 62                                                                       -1173                                                                               2 × -83,                                                                       6 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1584 kJ                                       mol.sup.-1.                                       __________________________________________________________________________

The `times four` criterion is met for [II-80] even without considering the kinetic energy of the monofluorines. Thus, the O/NO₂ +F procedure works well for the removal of all calcium species.

5. STRONTIUM

The enthalpy of sublimation of strontium fluoride is 451 kJ mol⁻¹, and the `times four` criterion is 1804 kJ mol⁻¹.

    __________________________________________________________________________     [II-81]                                                                            Sr(cr) + 2O(g) + 2NO.sub.2 (g) → Sr(NO.sub.3).sub.2 (cr)            0       2 × 249                                                                       2 × 33                                                                        -978,      ΔH.sub.r.sup.0 (298 K.) = -1542 kJ                                       mol.sup.-1                                        0       2 × 232                                                                       2 × 51                                                                        -780,      ΔG.sub.r.sup.0 (298 K.) = -1346 kJ                                       mol.sup.-1,                                       [II-82]                                                                            SrO(cr) + O(g) + 2nO.sub.2 (g) → Sr(NO.sub.3).sub.2 (cr)            -592    249  2 × 33                                                                        -978,      ΔH.sub.r.sup.0 (298 K.) = -701 kJ                                        mol.sup.-1                                        -561    232  2 × 51                                                                        -780,      ΔG.sub.r.sup.0 (298 K.) = -553 kJ                                        mol.sup.-1,                                       [II-83]                                                                            SrCl.sub.2 (cr) + 6O(g) + 2NO.sub.2 (g) → Sr(NO.sub.3).sub.2            (cr) + 2ClO.sub.2 (g)                                                      -829    6 × 249                                                                       2 × 33                                                                        -978  2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1505 kJ                                       mol.sup.-1                                        -780    6 × 232                                                                       2 × 51                                                                        -780  2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1254 kJ                                       mol.sup.-1,                                       [II-84]                                                                            SrF.sub.2 (cr) + 6O(g) + 2NO.sub.2 (g) → Sr(NO.sub.3).sub.2             (cr) + 2FO.sub.2 (g)                                                       -1217   6 × 249                                                                       2 × 33                                                                        -978  2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1295 kJ                                       mol.sup.-1                                        -1165   6 × 232                                                                       2 × 51                                                                        -780  2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1055 kJ                                       mol.sup.-1                                        and                                                                            [II-85]                                                                            Sr(NO.sub.3).sub.2 (cr) + 2OF(g) → SrF.sub.2 (cr) + 2NF.sub.3           (g) + 6F.sub.2 O(g)                                                        -978    20 × 79                                                                       -1217                                                                               2 × -124                                                                       6 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1923 kJ                                       mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -5243 kJ                                            mol.sup.-1                                        -780    20 × 62                                                                       -1165                                                                               2 × -83                                                                        6 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1539 kJ                                       mol.sup.-1.                                       __________________________________________________________________________

The `times four` criterion is met for [II-85] even without considering the kinetic energy of the monofluorines. Thus the O/NO₂ +F procedure works well for the removal of all strontium species.

6. BARIUM

The enthalpy of sublimation of barium fluoride is 405 kJ mol⁻¹, and the `times four` criterion is 1620 kJ mol⁻¹.

    __________________________________________________________________________     [II-86]                                                                            Ba(cr) + 2O(g) + 2NO.sub.2 (g) → Ba(NO.sub.3).sub.2 (cr)            0       2 × 249                                                                       2 × 33                                                                        -992,      ΔH.sub.r.sup.0 (298 K.) = -1556 kJ                                       mol.sup.-1                                        0       2 × 232                                                                       2 × 51                                                                        -797,      ΔG.sub.r.sup.0 (298 K.) = -1368 kJ                                       mol.sup.-1,                                       [II-87]                                                                            BaO(cr) + O(g) + 2NO.sub.2 (g) → Ba(NO.sub.3).sub.2 (cr)            -548    249  2 × 33                                                                        -992,      ΔH.sub.r.sup.0 (298 K.) = 759 kJ                                         mol.sup.-1                                        -520    232  2 × 41                                                                        -797,      ΔG.sub.r.sup.0 (298 K.) = -611 kJ                                        mol.sup.-1,                                       [II-88]                                                                            BaCl.sub.2 (cr) + 6O(g) + 2NO.sub.2 (g) → Ba(NO.sub.3).sub.2            (cr) + 2ClO.sub.2 (g)                                                      -859    6 × 249                                                                       2 × 33                                                                        -992  2 ×  102,                                                                     ΔH.sub.r.sup.0 (298 K.) = -1489 kJ                                       mol.sup.-1                                        -810    6 × 232                                                                       2 × 51                                                                        -797  2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1241 kJ                                       mol.sup.-1,                                       [II-89]                                                                            BaF.sub.2 (cr) + 6O(g) + 2NO.sub.2 (g) → Ba(NO.sub.3).sub.2             (cr) + 2FO.sub.2 (g)                                                       -1209   6 × 249                                                                       2 × 33                                                                        -992  2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1317 kJ                                       mol.sup.-1                                        -1158   6 × 232                                                                       2 × 51                                                                        -797  2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1079 kJ                                       mol.sup.-1                                        and                                                                            [II-90]                                                                            Ba(NO.sub.3).sub.2 (cr) + 20F(g) → BaF.sub.2 (cr) + 2NF.sub.3           (g) + 6F.sub.2 O(g)                                                        -992    20 × 70                                                                       -1209                                                                               2 × -124                                                                       6 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1901 kJ                                       mol.sup.-1                                                                     ΔH.sub.r *(298 K.) = -5221 kJ                                            mol.sup.-1                                        -797    20 × 62                                                                       -1158                                                                               2 × -83                                                                        6 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) =-1515 kJ                                        mol.sup.-1.                                       __________________________________________________________________________

Once again we find that the `times four` criterion is met even without considering the kinetic energy of the monofluorines. Thus, the O/NO₂ +F procedure works well for the removal of all alkali metal and alkaline earth metal species.

D. Group IIIA.

1. INTRODUCTION

Whereas the elements of Groups IA and IIA would not be expected to be present on a wafer as the element or as an `alloy`, this is not the case for the elements of Group IIIA. Aluminium and aluminum-copper alloys are frequently used as electrical conductors. Elementary boron may be present as a by-product of ion implantation. Furthermore, there is a large family of III-V compound semiconductors.

In addition to the O/NO₂ and F reagents we shall introduce a third reagent--methyl. Methyl is generated by introducing an excess of methane into the monofluorine stream by means of the lower circle.

    ______________________________________                                         [II-91] CH.sub.4 (g) + F(g) → CH.sub.3 (g) + HF(g)                      ______________________________________                                         -75   79     146     -272, ΔH.sub.r.sup.0 (298 K.) = -130 kJ                                  mol.sup.-1                                                -51   62     148     -275, ΔG.sub.r.sup.0 (298 K.) = -138 kJ                                  mol.sup.-1.                                               ______________________________________                                    

For [II-91] k_(r) (298K)=8×10⁻¹¹ cm³ molecule ⁻¹ s⁻¹ <II-11>, <II-12>. Thus, reaction occurs with essentially every collision.

In Table II-3 are listed the enthalpies of formation of the methyl compounds of Groups IIB, IIIA, IVA, VA and VIA and their enthalpies of sublimation or vaporization. All of the data are from Ref. <B> except where specifically noted. The symbol `Me` represents the CH₃ radical.

Me₃ B, Me₃ N, MeO and Me₂ O are all gases at 298K. Me₃ requires an additional 39.9 kJ mol⁻¹ to volatilize by the criteria of [II-1]. All of the other compounds will self-volatilize by the criterion of [11-2]. (These comments, strictly speaking are not correct. The criteria apply to the free energies and not to the enthalpies.) .

                                      TABLE II-3                                   __________________________________________________________________________     METHYL COMPOUNDS                                                               THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)                                                  ΔH.sub.s.sup.0 (298 K.) or ΔH.sub.p.sup.0 (298 K.)                 (kJ mol.sup.-1)                                                                IIB     IIB     IVA       VA        VIA                                        __________________________________________________________________________                                         MeO(g) + 18*                                               28                                                                             Me.sub.4 C(cr) - 196**                                                 Me.sub.3 B(l) - 143                                                                    (l) - 190**                                                                              Me.sub.3 N(l) - 46                                           19      22        22                                                           (g) - 124                                                                              (g) - 168**                                                                              (g) - 24  Me.sub.2 O(g) - 184                                Me.sub.3 Al(l) - 136                                                                   Me.sub.4 Si(l) - 272***                                                                  Me.sub.3 P(l) - 129***                                                                   Me.sub.2 S(l) - 65                                 62      27        28        28                                                 (g) - 74                                                                               (g) - 245***                                                                             (g) - 101***                                                                             (g) - 37                                   Me.sub.2 Zn(l) + 23                                                                    Me.sub.3 Ga(l) - 78                                                                    Me.sub.4 Ge(l) - 98***                                                                   Me.sub.3 As(l) - 16***                               30      33      27        29                                                   (g) + 53                                                                               (g) - 45                                                                               (g) - 71***                                                                              (g) + 13***                                                  Me.sub.3 In(cr) +                                                              125***                                                                         48                                                                     Me.sub.2 Cd(l) + 64                                                                            Me.sub.4 Sn(l) - 5                                                                       Me.sub.3 Sb(l) + 1***                                38              33        31                                                   (g) + 102                                                                              (g) + 173***                                                                           (g) - 19  (g) + 32***                                          Me.sub.2 Hg(l) + 60                                                                            Me.sub.4 Pb(l) + 98                                                                      Me.sub.3 Bi(l) + 158***                              34              38        36                                                   (g) + 94        (g) + 136 (g) + 194***                                         __________________________________________________________________________      (*Ref. <II13>, **Ref. <II14>, ***Ref. <II15>).                           

The thermodynamic data for both Group III A and Group V A are presented her. This is because the analyses of the chemistries of the III-V compounds obviously require both sets of data.

                                      TABLE II-4                                   __________________________________________________________________________     GROUP IIIA                                                                     THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES                                                                               B       Al      Ga      In                                              __________________________________________________________________________     M.sub.2 O.sub.3                                                                    (cr)                                                                              -1272/-1193                                                                            -1676/-1582                                                                            1089*/-998*                                                                            -926*/-831*                                         (g)                                                                               -836/-825                                                               MO.sub.2                                                                           (g)                                                                               -285/-290                                                                              -86/-92                                                         MCl.sub.3                                                                          (cr)       -706/-630                                                                              -525*/-455*                                                                            -537*/--                                            (l)                                                                               -427*/-387*                                                                 (g)                                                                               -403/-388                                                                              -585/-570       -374*/--                                        MF  (g)                                                                               -116/-144                                                                              -266/-291                                                                              -252*/--                                                                               -203*/--                                        MF.sub.2                                                                           (g)                                                                               -590/-601                                                                              -695/-704                                                       MF.sub.3                                                                           (cr)       -1510/-1431                                                                            -1163*/-1085*                                               (g)                                                                               -1136/-1119                                                                            -1209/-1193                                                     MN  (cr)                                                                              -251/-225                                                                              -318/-287                                                                              -110*/--                                                                               -18*/--                                         MP  (cr)                                                                              -79*/-- -166*/--                                                                               -88*/-- -89*/-77*                                       MAs (cr)       -116*/--                                                                               -71*/-68*                                                                              -59*/-54*                                       MSb (cr)               -42*/-39*                                                                              -30*/-26*                                       __________________________________________________________________________      (*Ref. <B>).                                                             

                                      TABLE II-5                                   __________________________________________________________________________     GROUP VA                                                                       THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES                                                                               N     P       As       Sb       Bi                                      __________________________________________________________________________     MO  (g)                                                                               +90/+87                                                                              -24/-47  +70a/-- +199a/--                                         M.sub.2 O.sub.3                                                                    (cr)                               -574a/- 494a                            M.sub.2 O.sub.4                                                                    (cr)             -794a/--                                                  M.sub.2 O.sub.5                                                                    (cr)             -925a/- 782a                                                                   -1441a/- 1268a                                            M.sub.4 O.sub.6                                                                    (cr)             -1314a/- 1152a                                                (g)      -2214/-2085                                                                            -1209a/- 1098a                                            MO.sub.2                                                                           (g)                                                                               +33/+51                                                                              -315/317                                                          M.sub.4 O.sub.10                                                                   (cr)     -3010/- 2723                                                          (g)      -2904/- 2670                                                      MO.sub.3                                                                           (g)                                                                               +71/+ 116                                                               MCl.sub.3                                                                          (cr)                      -382a/-324a                                                                             -379a/-  315a                               (l)                                                                               +230a/--                                                                             -320a/-272a                                                                            -308a/- 259a                                                  (g)      -287a/-268a                                                                            -262a/-249a                                                                             -314a/-301a                                                                             -266a/- 256a                            MCl.sub.5                                                                          (cr)     -444a/--                                                              (l)                       -440a/- 350a                                         (g)      -375a/-305a      -394a/- 334a                                     MF.sub.3                                                                           (cr)                      -916a/-- -904b/- 940b                                                 -821a/- 774a                                                  (l)                                                                            (g)                                                                               -132/-91                                                                             -958/-937                                                                              -786a/-771a                                                                             -47a/--                                          __________________________________________________________________________      (a Ref. <B>, b Ref. <II17>)                                              

It should be noted that the nitrates of aluminum, gallium and indium exist only as the hydrates. On dehydration they decompose to the oxides.

3. BORON

The only boron compounds listed in TABLE II-4 which are not gases at 289K are B₂ O₃, BN and BP.

    __________________________________________________________________________     [II-92]                                                                            B(cr) + 1.5O(g) → 0.5B.sub.2 O.sub.3 (cr)                           0          1.5 × 249                                                                      0.5 × -1272,                                                                            ΔH.sub.r.sup.0 (298 K.) = -1010 kJ                                       mol.sup.-1                                     0          1.5 × 232                                                                      0.5 × -1193,                                                                            ΔG.sub.r.sup.0 (298 K.) = -974 kJ                                        mol.sup.-1,                                    [II-93]                                                                            0.5B.sub.2 O.sub.3 (cr) + 0.5O(g) → BO.sub.2 (g)                    0.5 × -1272                                                                         0.5 × 249                                                                      -285,          ΔH.sub.r.sup.0 (298 K.) = +226 kJ                                        mol.sup.-1                                     0.5 × -1193                                                                         0.5 × 232                                                                      -290           ΔG.sub.r.sup.0 (298 K.) = +190 kJ                                        mol.sup.-1,                                    [II-94]                                                                            BN(cr) + 3.5O(g) → 0.5B.sub.2 O.sub.3 (cr) + NO.sub.2 (g)           -251       3.5 × 249                                                                      0.5 × -1272                                                                     +31,    ΔH.sub.r.sup.0 (298 K.) = -1226 kJ                                       mol.sup.-1                                     -225       3.5 × 232                                                                      0.5 × -1193                                                                     +51,    ΔG.sub.r.sup.0 (298 K.) = -1132 kJ                                       mol.sup.-1                                     and                                                                            [II-95]                                                                            BP(cr) + 4O(g) → 0.5N.sub.2 O.sub.3 (cr) + 0.25P.sub.4                  O.sub.10 (cr)                                                              -79        4 × 249                                                                        0.5 × -1272                                                                     0.25 × -3010,                                                                    ΔH.sub.r.sup.0 (298 K.) = -2306 kJ                                       mol.sup.-1.                                    __________________________________________________________________________

In all of these reactions boric oxide remains as a residue. In [II-95 the phosphorus oxide will volatilize since the `times four` criterion is 106 kJ/mole of BP.

    __________________________________________________________________________     [II-96]                                                                            B(cr) + 3F(g) → BF.sub.3 (g)                                        0       3 × 79                                                                        -1136       ΔH.sub.r.sup.0 (298 K.) = -1373 kJ                                       mol.sup.-1                                            0       3 × 62                                                                        -1119       ΔG.sub.r.sup.0 (298 K.) = -1305 kJ                                       mol.sup.-1,                                           [II-97]                                                                            B.sub.2 O.sub.3 (cr) + 12F(g) → 2BF.sub.3 (g) + 3F.sub.2 O(g)       -1272   12 × 79                                                                       2 × -1136                                                                      3 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1876 kJ                                       mol.sup.-1                                            -1193   12 × 62                                                                       2 × -1119                                                                      3 × 42,                                                                        ΔG.sub.r.sup.0 (298 K.) = -1663 kJ                                       mol.sup.-1,                                           [II-98]                                                                            BN(cr) + 6F(g) → BF.sub.3 (g) + NF.sub.3 (g)                        -251    6 × 79                                                                        -1136 -132, ΔH.sub.r.sup.0 (298 K.) = -1491 kJ                                       mol.sup.-1                                            -225    6 × 62                                                                        -119  -91,  ΔG.sub.r.sup.0 (298 K.) = -1357 kJ                                       mol.sup.-1,                                           [II-99]                                                                            BP(cr) + 6F(g) → BF.sub.3 (g) + PF.sub.3 (g)                        -79     6 × 79                                                                        -1136 -958, ΔH.sub.r.sup.0 (298 K.) = -2489 kJ                                       mol.sup.-1,                                           [II-100]                                                                           B(Cr) + 3CH.sub.3 (g) → (CH.sub.3).sub.3 B(g)                       0       3 × 146                                                                       2 × -124,                                                                            ΔH.sub.r.sup.0 (298 K.) = -686 kJ                                        mol.sup.-1,                                           [II-101]                                                                           B.sub.2 O.sub.3 (cr) + 12CH.sub.3 (g) → 2(CH.sub.3).sub.3 B(g)          + (CH.sub.3).sub.2 O(g)                                                    -1272   12 × 146                                                                            3 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1280 kJ                                       mol.sup.-1,                                           [II-102]                                                                           BN(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 B(g) +  (CH.sub.3)            .sub.3 N(g)                                                                -251    6 × 146                                                                       -124  -24,  ΔH.sub.r.sup.0 (298 K.) = -773 kJ                                        mol.sup.-1                                            and                                                                            [II-103]                                                                           BP(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 B(g)                          + (CH.sub.3).sub.3 P(g)                                                    -79     6 × 146                                                                       -124  -101, ΔH.sub.r.sup.0 (298 K.) = -1022 kJ                                       mol.sup.-1.                                           __________________________________________________________________________

Thus, there are four procedures which are effective in volatilizing all of the boron species present:

    ______________________________________                                                      O + F                                                                          F                                                                              O + Me                                                                         Me.                                                               ______________________________________                                    

4. ALUMINUM

None of the aluminum compounds meet the criteria of either [II-1] or [II-2]. We must, therefore, depend on the `times four` criterion. For aluminum fluoride it is 1204 kJ mol⁻¹. For trimethyl aluminum it is 248 kJ mol⁻¹.

    __________________________________________________________________________     [II-104]                                                                           Al(cr) + 1.5O(g) → 0.5Al.sub.2 O.sub.3 (cr)                         0       1.5 × 249                                                                      0.5 × -1676,                                                                            ΔH.sub.r.sup.0 (298 K.) = -1212 kJ                                       mol.sup.-1,                                       0       1.5 × 232                                                                      0.5 × -1582,                                                                            ΔG.sub.r.sup.0 (298 K.) = -1139 kJ                                       mol.sup.-1,                                       [II-105]                                                                           AlCl.sub.3 (cr) + 7.5O(g) → 0.5Al.sub.2 O.sub.3 (cr) +                  3ClO.sub.2 (g)                                                             -706    7.5 × 249                                                                      0.5 × -1676                                                                     3 × 102,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1694 kJ                                       mol.sup.-1                                        -630    25 × 232                                                                       0.5 × -1582                                                                     3 × 120,                                                                         ΔG.sub.r.sup.0 (298 K.) = -1541 kJ                                       mol.sup.-1,                                       [II-106]                                                                           AlF.sub.3 (cr) + 7.5O(g) → 0.5Al.sub.2 O.sub.3 (cr)                     + 3FO.sub.2 (g)                                                            -1510   7.5 × 249                                                                      0.5 × -1676                                                                     3 × 13,                                                                           ΔH.sub.r.sup.0 (298 K.) = -1156 kJ                                      mol.sup.-1                                        -1431   7.5 × 232                                                                      0.5 × -1582                                                                     3 × 27,                                                                          ΔG.sub.r.sup.0 (298 K.) = -1019 kJ                                       mol.sup.-1,                                       [II-107]                                                                           AlN(cr) + 3.5O(g) → 0.5Al.sub.2 O.sub.3 (cr) + NO.sub.2 (g)         -318    3.5 × 249                                                                      0.5 × -1676                                                                     33,     ΔH.sub.r.sup.0 (298 K.) = -1398 kJ                                       mol.sup.-1                                        -287    3.5 × 232                                                                      0.5 × -1582                                                                     51,     ΔG.sub.r.sup.0 (298 K.) = -1265 kJ                                       mol.sup.-1,                                       [II-108]                                                                           AlP(cr) + 4O(g) → 0.5Al.sub.2 O.sub.3 (cr) + 0.25P.sub.4                O.sub.10 (cr)                                                              -166    4 × 249                                                                        0.5 × -1676                                                                     0.25 × -3010,                                                                    ΔH.sub.r.sup.0 (298 K.) = -2420 kJ                                       mol.sup.-1                                        and                                                                            [II-109]                                                                           AlAs(cr) + 3O(g) → 0.5Al.sub.2 O.sub.3 (cr) + 0.25As.sub. 4             O.sub.6 (cr)                                                               -116    3 × 249                                                                        0.5 × -1676                                                                     0.25 × -1314,                                                                    ΔH.sub.r.sup.0 (298 K.) = -1798 kJ                                       mol.sup.-1.                                       [II-110]                                                                           Al(cr) + 3F(g) → AlF.sub.3 (cr)                                     0       3 × 79                                                                         -1510,         ΔH.sub.r.sup.0 (298 K.) = -1747 kJ                                       mol.sup.-1                                        0       3 × 62                                                                         -1431,         ΔG.sub.r.sup.0 (298 K.) = -1617 kJ                                       mol.sup.-1,                                       [II-111]                                                                           Al.sub.2 O.sub.3 (cr) + 12F(g) → 2AlF.sub.3 (cr) + 3F.sub.2             O(g)                                                                       -1676   12 × 79                                                                        2 × -1510                                                                       3 × 24,                                                                          ΔH.sub.r.sup.0 (298 K.) = -2220 kJ                                       mol.sup.-1                                        -1582   12 × 62                                                                        2 × -1431                                                                       3 × 42,                                                                          ΔG.sub.r.sup.0 (298 K.) = -1898 kJ                                       mol.sup.-1,                                       (This reaction is 94 kJ mol.sup.-1 of AlF.sub.3 below the `times four`         criterion.)                                                                    [II-112]                                                                           P.sub.4 O.sub.10 (cr) + 32F(g) → 4PF.sub.3 (g) + 10F.sub.2              O(g)                                                                       -3010   32 × 79                                                                        4 × -958                                                                        10 × 24,                                                                         ΔH.sub.r.sup.0 (298 K.) = -3110 kJ                                       mol.sup.-1                                        -2723   32 × 62                                                                        4 × -959                                                                        10 × 42,                                                                         ΔG.sub.r.sup.0 (298 K.) = -2589 kJ                                       mol.sup.-1,                                       [II-113]                                                                           As.sub.4 O.sub.6 (cr) + 24F(g) → 4AsF.sub.3 (g) + 6F.sub.2              O(g)                                                                       -1314   24 × 79                                                                        4 × -786                                                                        6 × 24,                                                                          ΔH.sub.r.sup.0 (298 K.) = -3582 kJ                                       mol.sup.-1                                        -1152   24 × 62                                                                        4 × -770                                                                        6 × 42,                                                                          ΔG.sub.r.sup.0 (298 K.) = -3164 kJ                                       mol.sup.-1,                                       [II-114]                                                                           AlN(cr) + 6F(g) → AlF.sub.3 (cr) + NF.sub.3 (g)                     -318    6 × 79                                                                         -1510  -132,   ΔH.sub.r.sup.0 (298 K.) = -1798 kJ                                       mol.sup.-1                                        -287    6 × 62                                                                         -1431  -91,    ΔG.sub.r.sup.0 (298 K.) = -1607 kJ                                       mol.sup.-1,                                       [II-115]                                                                           AlP(cr) + 6F(g) → AlF.sub.3 (cr) + PF.sub.3 (g)                     -166    6 × 79                                                                         -1510  -958,                                                                              ΔH.sub.r.sup.0 (298 K.) = -2776 kJ                                       mol.sup.-1                                            and                                                                            [II-116]                                                                           AlAs(cr) + 6F(g) → AlF.sub.3 (cr) + AsF.sub.3 (l)                   -116    6 × 79                                                                         -1510  -821,                                                                              ΔH.sub.r.sup.0 (298 K.) = -2689 kJ                                       mol.sup.-1.                                           __________________________________________________________________________

The `times four` criterion for arsenic trifluoride is 140 kJ mol⁻¹. Thus, the `times four` criterion for [II-109] is 1204+140=1444 kJ mol⁻¹. Monofluorine is therefore, an effective volatilizing reagent for [II-110-[II-116].

    __________________________________________________________________________     [II-117]                                                                           Al(cr) + 3CH.sub.3 (g) → (CH.sub.3).sub.3 Al(l)                     0       3 × 146                                                                       -136,       ΔH.sub.r.sup.0 (298 K.) = -574 kJ                                        mol.sup.-1,                                           [II-118]                                                                           Al.sub.2 O.sub.3 (cr) + 12CH.sub.3 (g) → 2(CH.sub.3).sub.3              Al(l) + 3(CH.sub.3).sub.2 O(g)                                             -1676   12 × 146                                                                      2 × -136                                                                       3 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -900 kJ                                        mol.sup.-1,                                           [II-119]                                                                           P.sub.4 O.sub.10 (cr) + 32CH.sub.3 (g) → 4(CH.sub.3)P(g) +              10(CH.sub.3).sub.2 O(g)                                                    -3010   32 × 146                                                                      4 × -101                                                                       10 × -184,                                                                     ΔH.sub.r.sup.0 (298 K.) = -3906 kJ                                       mol.sup.-1,                                           [II-120]                                                                           As.sub.4 O.sub.6 (cr) + 24CH.sub.3 (g) → 4(CH.sub.3)As(g) +             6(CH.sub.3)2O(g)                                                           -1314   24 × 146                                                                      4 × 13                                                                         6 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3242 kJ                                       mol.sup.-1,                                           [II-121]                                                                           AlN(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Al(l)                        + (CH.sub.3).sub.3 N(g)                                                    -318    6 × 146                                                                       -136  -24,  ΔH.sub.r.sup.0 (298 K.) = -718 kJ                                        mol.sup.-1,                                           [II-122]                                                                           AlP(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Al(l)                        + (CH.sub.3).sub.3 P(g)                                                    -166    6 × 146                                                                       -136  -101, ΔH.sub.r.sup.0 (298 K.) = -947 kJ                                        mol.sup.-1                                            and                                                                            [II-123]                                                                           AlAs(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Al(l)                       + (CH.sub.3).sub.3 As(g)                                                   -116    6 × 146                                                                       -136  +13,  ΔH.sub.r.sup.0 (298 K.) = -883 kJ                                        mol.sup.-1.                                           __________________________________________________________________________

Thus, we again find the quartet of effective procedures,

    ______________________________________                                         O + F,       F (cf. note after [II-111])                                       O + Me,      Me.                                                               ______________________________________                                    

5. GALLIUM

Except for trimethylgallium we do not have sufficient data to determine volatilization criteria. For trimethylgallium the `times four` criterion is 132 kJ mol⁻¹. Because of the lack of adequate thermodynamic data, we shall not carry out the monofluorine analyses. The reactions of methyl with the phosphorous and arsenic oxides are given above ([II-119] and [II-120]) and will not be repeated here.

    __________________________________________________________________________     [II-124]                                                                           Ga(c) + 1.5O(g) → 0.5Ga.sub.2 O.sub.3 (cr)                          0          1.5 × 249                                                                             0.5 × -1089,                                                                     ΔH.sub.r.sup.0 (298 K.) = -918 kJ                                        mol.sup.-1                                     0          1.5 × 232                                                                             0.5 × -998,                                                                      ΔG.sub.r.sup.0 (298 K.) = -847 kJ                                        mol.sup.-1,                                    [II-125]                                                                           GaCl.sub.3 (cr) + 7.5O(g) → 0.5Ga.sub.2 O.sub.3 (cr) +                  3ClO.sub.2 (g)                                                             -525       7.5 × 249                                                                      0.5 × -1089                                                                     3 × 102,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1581 kJ                                       mol.sup.-1                                     -455       7.5 × 232                                                                      0.5 × -998                                                                      3 × 120,                                                                         ΔG.sub.r.sup.0 (298 K.) = -1424 kJ                                       mol.sup.-1,                                    [II-126]                                                                           GaF.sub.3 (cr) + 7.5O(g) → 0.5Ga.sub.2 O.sub.3 (cr)                     + 3FO.sub.2 (g)                                                            -1163      7.5 × 249                                                                      0.5 × -1089                                                                     3 × 13,                                                                          Δ H.sub.r.sup.0 (298 K.) = -1210 kJ                                      mol.sup.-1                                     -1085      7.5 × 232                                                                      0.5 × -998                                                                      3 × 27,                                                                          ΔG.sub.r.sup.0 (298 K.) = -1073 kJ                                       mol.sup.-1,                                    [II-127]                                                                           GaN(cr) + 3.5O(g) → 0.5Ga.sub.2 O.sub.3 (cr) + NO.sub.2 (g)         -110       3.5 × 249                                                                      0.5 × -1087                                                                     33,     ΔH.sub.r.sup.0 (298 K.) = -1273 kJ                                       mol.sup.-1,                                    [II-128]                                                                           GaP(Cr) + 4O(g) → 0.5Ga.sub.2 O.sub.3 (cr) + 0.25P.sub.4                O.sub.10 (cr)                                                              -88        4 × 249                                                                        0.5 × -1089                                                                     0.25 × -3010,                                                                    ΔH.sub.r.sup.0 (298 K.) = -2205 kJ                                       mol.sup.-1,                                    [II-129]                                                                           GaAs(cr) + 3O(g) → 0.5Ga.sub.2 O.sub.3 (cr) + 0.25Al.sub.4              O.sub.6 (cr)                                                               -71        3 × 247                                                                        0.5 × 1089                                                                      0.25 × -1314,                                                                    ΔH.sub.r.sup.0 (298 K.) = -1549 kJ                                       mol.sup.-1,                                    and                                                                            [II-130]                                                                           GaSb(cr) + 3O(g) → 0.5Ga.sub.2 O.sub.3 (cr) + 0.25Sb.sub.4              O.sub.6 (cr)                                                               -42        3 × 247                                                                        0.5 × -1089                                                                     0.25 × -1441,                                                                    ΔH.sub.r.sup.0 (298 K.) = -1610 kJ                                       mol.sup.-1.                                    [II-131]                                                                           Ga(cr) + 3CH.sub.3 (g) → (CH.sub.3).sub.3 Ga(l)                     0          3 × 146                                                                        -78,           ΔH.sub.r.sup.0 (298 K.) = -516 kJ                                        mol.sup.-1,                                    [II-132]                                                                           0.5Ga.sub.2 O.sub.3 (cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3             Ga(l) + 1.5(CH.sub.3).sub.2 O(g)                                           0.5 × -1089                                                                         6 × 146                                                                        -78    1.5 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -686 kJ                                        mol.sup.-1,                                    [II-133]                                                                           GaCl.sub.3 (cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Ga(l) +              3CH.sub.3 Cl(g)                                                            -525       6 × 146                                                                        -78    3 × -84,                                                                         ΔH.sub.r.sup.0 (298 K.) = -681 kJ                                        mol.sup.-1,                                    [II-134]                                                                           GaF.sub.3 (cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Ga(l) +               3CH.sub.3 F(g)                                                             -1163      6 × 146                                                                        -78    3 × -234,                                                                        ΔH.sub.r.sup.0 (298 K.) = -493 kJ                                        mol.sup.-1,                                    [II-135]                                                                           GaN(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Ga(l)                        + (CH.sub.3).sub.3 N(g)                                                    -110       6 × 146                                                                        -78    -24,    ΔH.sub.r.sup.0 (298 K.) = -868 kJ                                        mol.sup.-1,                                    [II-136]                                                                           GaP(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Ga(l)                        + (CH.sub.3).sub.3 P(g)                                                    -88        6 × 146                                                                        -78    -101,   ΔH.sub.r.sup.0 (298 K.) = -967 kJ                                        mol.sup.-1,                                    [ II-137]                                                                          GaAs(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 (Ga(l)                      + (CH.sub.3).sub.3 As(g)                                                   -71        6 × 146                                                                        -78    13,     ΔH.sub.r.sup.0 (298 K.) = -870 kJ                                        mol.sup.-1,                                    [II-138]                                                                           GaSb(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Ga(l)                       + (CH.sub.3).sub.3 Sb(g)                                                   -42        6 × 146                                                                        -78    32,     ΔH.sub.r.sup.0 (298 K.) = -880 kJ                                        mol.sup.-1                                     and                                                                            [II-139]                                                                           Sb.sub.4 O.sub.6 (cr) + 24CH.sub.3 (g) → 4(CH.sub.3).sub.3 Sb           + 6(CH.sub.3).sub.2 O(g)                                                   -1441      24 × 146                                                                       4 × 32                                                                          6 × -184,                                                                        ΔH.sub.r.sup.0 (298 K.) = -3039 kJ                                       mol.sup.-1.                                    __________________________________________________________________________

Thus, we have two effective procedures. O+Me and Me.

6. INDIUM

The `times four` criterion for trimethylindium is 192 kJ mol⁻¹. Again because of the lack of adequate thermodynamic data, we shall not carry out the monofluorine analyses.

    __________________________________________________________________________     [II-140]                                                                           In(cr) + 1.5O(g) → 0.5In.sub.2 O.sub.3 (cr)                         0          1.5 × 249                                                                      0.5 × -926,                                                                             ΔH.sub.r.sup.0 (298 K.) = -837 kJ                                        mol.sup.-1                                     0          1.5 × 232                                                                      0.5 × -831,                                                                             ΔG.sub.r.sup.0 (298 K.) = -764 kJ                                        mol.sup.-1,                                    [II-141]                                                                           InCl.sub.3 (cr) + 7.5O(g) → 0.5In.sub.2 O.sub.3 (cr) +                  3ClO.sub.2 (g)                                                             -537       7.5 × 249                                                                      0.5 × -926                                                                      3 × 102,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1488 kJ                                       mol.sup.-1,                                    [II-142]                                                                           InN(cr) + 3.5O(g) → 0.5In.sub.2 O.sub.3 (cr) + NO.sub.2 (g)         -18        3.5 × 249                                                                      0.5 × -926                                                                      33,     ΔH.sub.r.sup.0 (298 K.) = -1284 kJ                                       mol.sup.-1,                                    [II-143]                                                                           InP(cr) + 3.5O(g) → 0.5In.sub.2 O.sub.3 (cr) + 0.25P.sub.4              O.sub.10 (cr)                                                              -88        3.5 × 249                                                                      0.5 × -926                                                                      0.25 × 3010,                                                                     ΔH.sub.r.sup.0 (298 K.) = -1999 kJ                                       mol.sup.-1,                                    [II-144]                                                                           InAs(cr) + 3.5O(g) → 0.5In.sub.2 O.sub.3 (cr) + 0.25 As.sub.4           O.sub.6 (cr)                                                               -59        3.5 × 249                                                                      0.5 × -926                                                                      0.25 × -1314,                                                                    ΔH.sub.r.sup.0 (298 K.) = -1604 kJ                                       mol.sup.-1                                     and                                                                            [II-145]                                                                           InSb + 3.5O(g) → 0.5In.sub.2 O.sub.3 (cr) + 0.25Sb.sub.4                O.sub.6 (cr)                                                               -30        3.5 × 249                                                                      0.3 × -926                                                                      0.25 × -1441,                                                                    ΔH.sub.r.sup.0 (298 K.) = -1665 kJ                                       mol.sup.-1.                                    [II-146]                                                                           In(cr) + 3CH.sub.3 (g) → (CH.sub.3).sub.3 In(cr)                    -0         3 × 146                                                                               125,    ΔH.sub.r.sup.0 (298 K.) = -313 kJ                                        mol.sup.-1,                                    [ II-147]                                                                          In.sub.2 O.sub.3 (cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3                In(cr) + 1.5(CH.sub.3).sub.2 O(g)                                          0.5 × -926                                                                          6 × 146                                                                        125    1.5 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -564 kJ                                        mol.sup.-1,                                    [II-148]                                                                           InCl.sub.3 (cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 In(cr) +             3CH.sub.3 Cl(g)                                                            -537       6 × 146                                                                        125    3 × -84,                                                                         ΔH.sub.r.sup.0 (298 K.) = -466 kJ                                        mol.sup.-1,                                    [II-149]                                                                           InN(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 In(cr)                       + (CH.sub.3).sub.3 N(g)                                                    -18        6 × 146                                                                        125    -24,    ΔH.sub.r.sup.0 (298 K.) = -757 kJ                                        mol.sup.-1,                                    [II-150]                                                                           InP(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 In(cr)                       + (CH.sub.3).sub.3 P(g)                                                    -88        6 × 146                                                                        125    -101,   ΔH.sub.r.sup.0 (298 K.) = -764 kJ                                        mol.sup.-1,                                    [II-151]                                                                           InAs(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 In(cr)                      + (CH.sub.3).sub.3 As(g)                                                   -59        6 × 146                                                                        125  13,       ΔH.sub.r.sup.0 (298 K.) = -679 kJ                                        mol.sup.-1                                     and                                                                            [II-152]                                                                           InSb(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 In(cr)                      + (CH.sub.3).sub.3 In(cr) + (CH.sub.3).sub.3 Sb(g)                         -30        6 × 146                                                                        125    -32,    ΔH.sub.r.sup.0 (298 K.) = -689 kJ                                        mol.sup.-1.                                    __________________________________________________________________________

Again we have two effective procedures

O+Me and Me.

E. Group IV A.

1. INTRODUCTION

At this point we have introduced three reagants O/NO₂, F and Me. In terms of upper circle/lower circle reagents they are

    ______________________________________                                         UPPER CIRCLE   LOWER CIRCLE                                                    ______________________________________                                         O.sub.2        NO.sub.2 (O.sub.2 *)                                            F.sub.2        --                                                              F.sub.2        CH.sub.4                                                        ______________________________________                                          (*O.sub.2 is used in the lower circle as a diluent when photoresists are       removed to prevent overheating of the wafer.)                            

Although this three step process is adequate for the removal of Group IVA elements and compounds, we shall introduce monohydrogen as a useful alternative reagent. The three step process leaves the surface `dangling bonds` attached to fluorine atoms. If a deposition is to be made on the freshly cleaned surface, it is more desirable that the surface atoms be bonded to hydrogens rather than fluorines.

2. THERMODYNAMIC DATA

                                      TABLE II-6                                   __________________________________________________________________________     GROUP IVA                                                                      THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES                                                                              C      Si      Ge      Sn      Pb                                        __________________________________________________________________________     Diamond                                                                              1.9*/2.9*                                                                MO (cr)              -262*/-237*                                                                            -286*/-257*                                                                            -217*/-188*                                  (g)                                                                               -110/-137                                                                             -100/-127                                                                              -46*/-73*                                                                              +15*/-8*                                          MO.sub.2                                                                          (cr)      -911/-856                                                                              -551*/-497*                                                                            -581*/-520*                                                                            -277*/-217*                                  (g)                                                                               -394/-394                                                                MF (g)                                                                               +255/+223                                                                             -20/-52 -33*/--                                                   MF.sub.2                                                                          (cr)                              -664*/-617*                                  (g)                                                                               -182/-192                                                                             -588/-598                                                                              ˜-500*/--                                           MF.sub.3                                                                          (g)                                                                               -470/-457                                                                             -1085/-1573                                                       MF.sub.4                                                                          (cr)                              -942*/--                                     (g)                                                                               -933/-888                                                                             -1615/-1573                                                       MH (g)                                                                               +594/+561                                                                             +377/+343                                                         MH.sub.2                                                                          (g)                                                                               +386/+369                                                                             +245**/--                                                         MH.sub.3                                                                          (g)                                                                               +146/+148                                                                             +209**/--                                                         MH.sub.4                                                                          (g)                                                                               -75/-51                                                                               +34/+57 +91*/+113*                                                                             +163*/+188*                                       __________________________________________________________________________      (*Ref. <B>, **Ref. < II16>).                                             

3. CARBON

    ______________________________________                                         [II-153]                                                                             C(graphite) + O(g) → CO(g)                                        0        249     -110, ΔH.sub.r.sup.0 (298 K.) = -359 kJ                                  mol.sup.-1                                                    0        232     -137, ΔG.sub.r.sup.0 (298 K.) = -369 kJ                                  mol.sup.-1,                                                   [II-154]                                                                             C(graphite) + 2O(g) → CO.sub.2 (g)                                0       2 × 249                                                                           -394, ΔH.sub.r.sup.0 (298 K.) = -892 kJ                                  mol.sup.-1                                                    0       2 × 232                                                                           -394, ΔG.sub.r.sup.0 (298 K.) = -858 kJ                                  mol.sup.-1,                                                   [II-155]                                                                             C(graphite) + F(g) → CF(g)                                        0         79     255, ΔH.sub.r.sup.0 (298 K.) = +116 kJ mol.sup.-1       0         62     223, ΔG.sub.r.sup.0 (298 K.) = +161 kJ                                   mol.sup.-1,                                                   [II-156]                                                                             C(graphite) + 2F(g) → CF.sub.2 (g)                                0        2 × 79                                                                           -182, ΔH.sub.r.sup.0 (298 K.) = -340 kJ                                  mol.sup.-1                                                    0        2 × 62                                                                           -192, ΔG.sub.r.sup.0 (298 K.) = -316 kJ                                  mol.sup.-1,                                                   [II-157]                                                                             C(graphite) + 3F(g) → CF.sub.3 (g)                                0        3 × 79                                                                           -470, ΔH.sub.r.sup.0 (298 K.) = -707 kJ                                  mol.sup.-1                                                    0        3 × 62                                                                           -457, ΔG.sub.r.sup.0 (298 K.) = -643 kJ                                  mol.sup.-1,                                                   [II-158]                                                                             C(graphite) + 4F(g) → CF.sub.4 (g)                                0       4 × 79                                                                           -933, ΔH.sub.r.sup.0 (298 K.) = -1249 kJ                                 mol.sup.-1                                                     0       4 × 62                                                                           -888, ΔG.sub.r.sup.0 (298 K.) = -1136 kJ                                 mol.sup.-1,                                                    [II-159]                                                                             C(graphite) + 4CH.sub.3 (g) → (CH.sub.3).sub.4 C(g)               0       4 × 146                                                                           -168, ΔH.sub.r.sup.0 (298 K.) = -751 kJ                                  mol.sup.-1,                                                   [II-160]                                                                             C(graphite) + H(g) → CH(g)                                        0        218     594, ΔH.sub.r.sup.0 (298 K.) = +376 kJ mol.sup.-1       0        203     561, ΔG.sub.r.sup.0 (298 K.) = +358 kJ                                   mol.sup.-1,                                                   [II-161]                                                                             C(graphite) + 2H(g) → CH.sub.2 (g)                                0        2 × 218                                                                           386, ΔH.sub.r.sup.0 (298 K.) = -50 kJ mol.sup.-1       0        2 × 203                                                                           369, ΔG.sub.r.sup.0 (298 K.) = -7 kJ mol.sup.-1,       [II-162]                                                                             C(graphite) + 3H(g) → CH.sub.3(g)                                 0        3 × 218                                                                           146, ΔH.sub.r.sup.0 (298 K.) = -508 kJ                                   mol.sup.-1                                                   0        3 × 203                                                                           148, ΔG.sub.r.sup.0 (298 K.) = -461 kJ                                   mol.sup.-1                                                   [II-163]                                                                             C(graphite) + 4H(g) → CH.sub.4 (g)                                0       4 × 218                                                                           -75, ΔH.sub.r.sup.0 (298 K.) = -947 kJ mol.sup.-1       0       4 × 203                                                                           -51, ΔG.sub.r.sup. 0 (298 K.) = -863 kJ                 ______________________________________                                                          mol.sup.-1.                                              

Although all of the calculations in this SECTION are for graphite, they are also valid for diamond since the enthalpy and free energy of formation of diamond are so small. Without thermodynamic data on the stepwise reactions, [II-159 must be considered as questionably effective. Only the reaction generating CO of the three possible diatomic products is thermodynamically favorable. None of these reactions, [II-153], [II-155] and [II-160], are kinetically favorable. The oxidation, fluoridation and hydrogenation of both graphite and diamond surfaces are well known phenomena. For the monofluorine and monohydrogen reactions at least two reagent-carbon bonds must be formed before a volatile product is generated. In some cases three or four reagent-carbon bonds are required. For the monoxygen case clearly two-carbon-oxygen single bonds (σ-bonds) will yield a volatile product.

4. SILICON

    __________________________________________________________________________     [II-164]                                                                           Si(cr) + O(g) → SiO(g)                                              0               -100, ΔH.sub.r.sup.0 (298 K.) = -349 kJ mol.sup.-1       0         232   -127, ΔG.sub.r.sup.0 (298 K.) = -359 kJ                                  mol.sup.-1,                                                    [II-165]                                                                           Si(cr) + 2O(g) → SiO.sub.2 (g)                                      0        2 × 249                                                                         -911, ΔH.sub.r.sup.0 (298 K.) = -1409 kJ                                 mol.sup.-1                                                     0        2 × 232                                                                         -856, ΔG.sub.r.sup.0 (298 K.) = -1320 kJ                                 mol.sup.-1,                                                    [II-166]                                                                           Si(cr) + F(g) → SiF(g)                                              0         79    -20, ΔH.sub.r.sup.0 (298 K.) = -99 kJ mol.sup.-1         0         62    -52, ΔG.sub.r.sup.0 (298 K.) = -114 kJ mol.sup.-1,       [II-167]                                                                           Si(cr) + 2F(g) → SiF.sub.2 (g)                                      0        2 × 79                                                                           -588, ΔH.sub.r.sup.0 (298 K.) = - 746 kJ                                 mol.sup.-1                                                    0        2 × 62                                                                           -598, ΔG.sub.r.sup.0 (298 K.) = -722 kJ                                  mol.sup.-1,                                                   [II-168]                                                                           Si(cr) + 3F(g) → SiF.sub.3 (g)                                      0        3 × 79                                                                         -1085, ΔH.sub.r.sup.0 (298 K.) = -1322 kJ                                mol.sup.-1                                                      0        3 × 62                                                                         -1073, ΔG.sub.r.sup.0 (298 K.) = -1259 kJ                                mol.sup.-1,                                                     [II-169]                                                                           Si(cr) + 4F(g) → SiF.sub.4 (g)                                      0        4 × 79                                                                         -1615, ΔH.sub.r.sup.0 (298 K.) = -1931 kJ                                mol.sup.-1                                                      0        4 × 62                                                                         -1593, ΔG.sub.r.sup.0 (298 K.) = -1841 kJ                                mol.sup.-1,                                                     [II-170]                                                                           SiO.sub.2 (cr) + 2F(g) → SiO(g) + F.sub.2 O(g)                      -911     2 × 79                                                                        -100 24, ΔH.sub.r.sup.0 (298 K.) = +677 kJ                                    mol.sup.-1                                                  -856     2 × 62                                                                        - 129                                                                               42, ΔG.sub.r.sup.0 (298 K.) = +647 kJ                                    mol.sup.-1,                                                 [II-171]                                                                           SiO.sub.2 (cr) + 4F(g) → Si(cr) + 2F.sub.2 O(g)                     -911     4 × 79                                                                        0  2 × 24, ΔH.sub.r.sup.0 (298 K.) = +643 kJ                          mol.sup.-1                                                    -856     4 × 62                                                                        0  2 × 42, ΔG.sub.r.sup.0 (298 K.) = +692 kJ                          mol.sup.-1,                                                   [II-172]                                                                           SiO.sub.2 (cr) + 5F(g) → SiF(g) + 2F.sub.2 O(g)                     -911     5 × 79                                                                        -20 2 × 24, ΔH.sub.r.sup.0 (298 K.) = +544 kJ                          mol.sup.-1                                                   -856     5 × 62                                                                        -52 2 × 42, ΔG.sub.r.sup.0 (298 K.) = +578 kJ                          mol.sup.-1,                                                  [II-173]                                                                           SiO.sub.2 (cr) + 6F(g) → SiF.sub.2 (g) + 2F.sub.2 O(g)              -911     6 × 79                                                                        -588                                                                                2 × 24, ΔH.sub.r.sup.0 (298 K.) = -103 kJ                         mol.sup.-1                                                   -856     6 × 62                                                                        -598                                                                               2 × 42, ΔG.sub.r.sup.0 (298 K.) = -30 kJ                           mol.sup.-1,                                                  [II-174]                                                                           SiO.sub.2 (cr) + 7F(g) → SiF.sub.3 (g) + 2F.sub.2 O(g)              -911     7 × 79                                                                       -1085                                                                               2 × 24, ΔH.sub.r.sup.0 (298 K.) = -679 kJ                          mol.sup.-1                                                   -856     7 × 62                                                                       -1073                                                                               2 × 42, ΔG.sub.r.sup.0 (298 K.) = -567 kJ                          mol.sup.-1,                                                  [II-175]                                                                           SiO.sub.2 (cr) + 8F(g) → SiF.sub.4 (g) + 2F.sub.2 O(g)              -911     8 × 79                                                                       -1615                                                                              2 × 24, ΔH.sub.r.sup.0 (298 K.) = -1288 kJ                         mol.sup.-1                                                    -856     8 × 62                                                                       -1573                                                                              2 × 42, ΔG.sub.r.sup.0 (298 K.) = -1129 kJ                         mol.sup.-1 ,                                                  [II-176]                                                                           Si(cr) + 4CH.sub.3 (g) → (CH.sub.3).sub.4 Si(g)                     0        4 × 146                                                                          -245, ΔH.sub.r.sup.0 (298 K.) = -829 kJ                                  mol.sup.-1,                                                   [II-177]                                                                           SiO.sub.2 (cr) + CH.sub.3 (g) → SiO(g) + CH.sub.3 O(g)              -911      146 -100 18, ΔH.sub.r.sup.0 (298 K.) = +683 kJ                                    mol.sup.-1,                                                 [II-178]                                                                           SiO.sub.2 (cr) + 2CH.sub.3 (g) → SiO(g) + (CH.sub.3).sub.2              O(g)                                                                       -911     2 × 146                                                                       -100 -184, ΔH.sub.r.sup.0 (298 K.) = +335 kJ                                  mol.sup.-1,                                                 [II-179]                                                                           SiO.sub.2 (cr) + 3CH.sub.3 (g) → Si(cr) + (CH.sub.3).sub.2              O(g) + CH.sub.3 O(g)                                                       -911    3 × 146                                                                        0 -184                                                                               18, ΔH.sub.r.sup.0 (298 K.) = +307 kJ                                    mol.sup.-1,                                                [II-180]                                                                           SiO.sub.2 (cr) + 4CH.sub.3 (g) → Si(cr) + 2(CH.sub.3).sub.2             O(g)                                                                       -911     4 × 146                                                                       0  2 × -184, ΔH.sub.r.sup.0 (298 K.) = -41 kJ                         mol.sup.-1,                                                   [II-181]                                                                           SiO.sub.2 (cr) + 8CH.sub.3 (g) → (CH.sub.3).sub.4 Si(g) +               2(CH.sub.3).sub.2 O(g)                                                     -911    8 × 146                                                                       -245                                                                               2 × -184, ΔH.sub.r.sup.0 (298 K.) = -870 kJ                        mol.sup.-1,                                                   [II-182]                                                                           Si(cr) + H(g) → SiH(g)                                              0         218    377, ΔH.sub.r.sup.0 (298 K.) = +159 kJ                                   mol.sup.-1,                                                   0         203    343, ΔG.sub.r.sup.0 (298 K.) = +140 kJ                                   mol.sup.-1,                                                   [II-183]                                                                           Si(cr) + 2H(g) → SiH.sub.2 (g)                                      0        2 × 218                                                                           245, ΔH.sub.r.sup.0 (298 K.) = -191 kJ mol.sup.-                         1,                                                           [II-184]                                                                           Si(cr) + 3H(g) → SiH.sub.3 (g)                                      0        3 × 218                                                                           209, ΔH.sub.r.sup.0 (298 K.) = -445 kJ                                   mol.sup.-1,                                                  [II-185]                                                                           Si(Cr) + 4H(g) → SiH.sub.4 (g)                                      0        4 × 218                                                                           34, ΔH.sub.r.sup.0 (298 K.) = -838 kJ mol.sup.-1       0        4 × 203                                                                           57, ΔG.sub.r.sup.0 (298 K.) = -755 kJ                                    mol.sup.-1,                                                  [II-186]                                                                           SiO.sub.2 (cr) + H(g) → SiO(g) + OH(g)                              -911      218 -100 39, ΔH.sub.r.sup.0 (298 K.) = +632 kJ                                    mol.sup.-1                                                  -856      203 -127 34, ΔG.sub.r.sup.0 (298 K.) = +560 kJ                                    mol.sup.-1,                                                 [II-187]                                                                           SiO.sub.2 (cr) + 2H(g) → SiO(g) + H.sub.2 O(g)                      -911     2 × 218                                                                       -100 -242, ΔH.sub.r.sup.0 (298 K.) =  +133 kJ                                 mol.sup.-1                                                  -856     2 × 203                                                                       -127 -229, ΔG.sub.r.sup.0 (298 K.) = +94 kJ                                   mol.sup.-1,                                                 [II-188]                                                                           SiO.sub.2 (cr) + 3H(g) → Si(cr) + H.sub.2 O(g) + OH(g)              -911    3 × 218                                                                       0  -242                                                                               39, ΔH.sub.r.sup.0 (298 K.) = +54 kJ                                     mol.sup.-1                                                 -856    3 × 203                                                                       0  -229                                                                               34, ΔG.sub.r.sup.0 (298 K.) = +52 kJ                                     mol.sup.-1,                                                [II-189]                                                                           SiO.sub.2 (cr) + 4H(g) → Si(cr) + 2H.sub.2 O(g)                     -911     4 × 218                                                                       0  2 × -242, ΔH.sub.r.sup.0 (298 K.) = -445 kJ                        mol.sup.-1                                                    -856     4 × 203                                                                       0  2 × -229, ΔG.sub.r.sup.0 (298 K.) = -414 kJ                        mol.sup.-1,                                                   [II-190]                                                                           SiO.sub.2 (cr) + 5H(g) → SiH(g) +  2H.sub.2 O(g)                    -911     5 × 218                                                                       377                                                                               2 × -242, ΔH.sub.r.sup.0 (298 K.) = -286 kJ                        mol.sup.-1                                                    -856     5 × 203                                                                       343                                                                               2 × -229, ΔG.sub.r.sup.0 (298 K.) = -274 kJ                        mol.sup.-1,                                                   [II-191]                                                                           SiO.sub.2 (cr) + 6H(g) → SiH.sub.2 (g) + 2H.sub.2 O(g)              -911     6 × 218                                                                       245                                                                               2 × -242, ΔH.sub.r.sup.0 (298 K.) = -636 kJ                        mol.sup.-1,                                                   [II-192]                                                                           SiO.sub.2 (cr) + 7H(g) → SiH.sub.3 (g) + 2H.sub.2 O(g)              -911     7 × 218                                                                       209                                                                               2 × -242, ΔH.sub.r.sup.0 (298 K.) = -890 kJ                        mol.sup.-1,                                                   and                                                                            [II-193]                                                                           SiO.sub.2 + 8H(g) → SiH.sub.4 (g) + 2H.sub.2 O(g)                   -911     8 × 218                                                                       34 2 ×  -242, ΔH.sub.r.sup.0 (298 K.) = -1283                         kJ mol.sup.-1                                                 -856     8 × 203                                                                       57 2 × -229, ΔG.sub.r.sup.0 (298 K.) = -1169 kJ                       mol.sup.-1.                                                   __________________________________________________________________________

Reactions [II-164] and [II-165 are expected to form a `surface crust` rather than a volatile compound or a `body` oxide. For kinetic reasons the reaction a monofluorine with silicon is not expected to yield a volatile species unless there are at least two fluorines per silicon. The reaction of monofluorine with silicon dioxide is not expected to yield a volatile silicon species unless there are at least six monofluorines per silicon dioxide.

In the absence of thermodynamic data on (CH₃)_(x) Si for x=1, 2, 3 definitive statements cannot be made with respect to the reactions of methyl with silicon or silicon dioxide. It is clear, however, that between four and eight methyls per silicon dioxide are required to yield a volatile silicon species.

A minimum of two monohydrogens per silicon is required for kinetic reasons as well as thermodynamic reasons for the production of a volatile silicon species. For kinetic reasons a minimum of six monohydrogens are required per silicon dioxide for the production of a volatile silicon species.

5. GERMANIUM

    __________________________________________________________________________     [II-194]                                                                           Ge(cr) + O(g) → GeO(cr)                                             0        249   -262, ΔH.sub.r.sup.0 (298 K.) = -511 kJ mol.sup.-1        0        232   -237, ΔG.sub.r.sup.0 (298 K.) = -469 kJ mol.sup.-1,       [II-195]                                                                           GeO(cr) + O(g) → GeO.sub.2 (cr)                                     -262      249  -551, ΔH.sub.r.sup.0 (298 K.) = -538 kJ mol.sup.-1        -237      232  -497, ΔG.sub.r.sup.0 (298 K.) = -492 kJ mol.sup.-1,       [II-196]                                                                           Ge(cr) + F(g) → GeF(cr)                                             0        79    -33, ΔH.sub.r.sup.0 (298 K.) = 112 kJ mol.sup.-1,         [II-197]                                                                           Ge(cr) + 2F(g) → GeF.sub.2 (cr)                                     0        2 × 79                                                                         -500, ΔH.sub.r.sup.0 (298 K.) = -658 kJ mol.sup.-1,       [II-198]                                                                           GeO(cr) + 3F(g) → GeF(g) + F.sub.2 O(g)                              -262    3 × 79                                                                        -33 24, ΔH.sub.r.sup.0 (298 K.) = +16 kJ mol.sup.-1,       [II-199]                                                                           GeO(cr) + 4F(g) → GeF.sub.2 (g) + F.sub.2 O(g)                      -262     4 × 79                                                                        -500                                                                               24, ΔH.sub.r.sup.0 (298 K.) = -530 kJ                                    mol.sup.-1,                                                  [II-200]                                                                           GeO.sub.2 (cr) + 5F(g) → GeF(g) + 2F.sub.2 O(g)                     -551     5 × 79                                                                       -33                                                                               2 × 24, ΔH.sub.r.sup.0 (298 K.) = +171 538 kJ                      mol.sup.-1,                                                    [II-201]                                                                           GeO.sub.2 (cr) + 6F(g) → GeF.sub.2 (g) + 2F.sub.2 O(g)              -551    6 × 79                                                                       -500                                                                               2 × 24, ΔH.sub.r.sup.0 (298 K.) = -375 kJ                          mol.sup.-1,                                                    [II-202]                                                                           Ge(cr) + 4CH.sub.3 (g) → (CH.sub.3).sub.4 Ge(g)                     0       4 ×  146                                                                         -71, ΔH.sub.r.sup.0 (298 K.) = -655 kJ mol.sup.-1,       [II-203]                                                                           GeO(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.4 Ge(g)                        + (CH.sub.3).sub.2 O(g)                                                    -262    6 × 146                                                                       -71                                                                               -184, ΔH.sub.r.sup.0 (298 K.) = -869 kJ                                  mol.sup.-1,                                                    [II-204]                                                                           GeO.sub.2 (Cr) + 8CH.sub.3 (g) → (CH.sub.3).sub.4 Ge(g) +               2(CH.sub.3).sub.2 O(g)                                                     -551    8 × 146                                                                       -71                                                                               2 × -184, ΔH.sub.r.sup.0 (298 K.) = -1056 kJ                       mol.sup.-1,                                                    [II-205]                                                                           Ge(cr) + 4H(g) → GeH.sub.4 (g)                                      0       4 × 218                                                                          91, ΔH.sub.r.sup.0 (298 K.) = -781 kJ mol.sup.-1         0       4 × 203                                                                          113, ΔG.sub.r.sup.0 (298 K.) = -699 kJ mol.sup.-1,       [II-206]                                                                           GeO(cr) + 6H(g) → GeH.sub.4 (g) + H.sub.2 O(g)                      -262    6 × 218                                                                        91                                                                               -242, ΔH.sub.r.sup.0 (298 K.) = -1197 kJ                                 mol.sup.-1                                                     -237    6 × 203                                                                       113                                                                               -229, ΔG.sub.r.sup.0 (298 K.) = -1097 kJ                                 mol.sup.-1,                                                    and                                                                            [II-207]                                                                           GeO.sub.2 (cr) + 8H(g) → GeH.sub.4 (g) + 2H.sub.2 O(g)              -551    8 × 218                                                                        91                                                                               2 × -242, ΔH.sub.r.sup.0 (298 K.) = -1586 kJ                       mol.sup.-1                                                     -497    8 × 203                                                                       113                                                                               2 × -229, ΔG.sub.r.sup.0 (298 K.) = -1472 kJ                       mol.sup.-1.                                                    __________________________________________________________________________

Thus, we find that monofluorine, methyl and monohydrogen are all effective reagents for the removal of all germanium species.

6. TIN

    __________________________________________________________________________     [II-208]                                                                           Sn(cr) + O(g) → SnO(cr)                                             0         248    -286, ΔH.sub.r.sup.0 (298 K.) = -534 kJ                                  mol.sup.-1                                                    0         232    -257, ΔG.sub.r.sup.0 (298 K.) = -489 kJ                                  mol.sup.-1,                                                   [II-209]                                                                           SnO(cr) + O(g) → SnO.sub.2 (g)                                      -286       248    -581, ΔH.sub.r.sup.0 (298 K.) = -544 kJ                                  mol.sup.-1                                                   -257       232    -520, ΔG.sub.r.sup.0 (298 K.) = -495 kJ                                  mol.sup.-1,                                                  [II-210]                                                                           Sn(cr) + 4CH.sub.3 (g) → (CH.sub.3).sub.4 Sn(g)                     0         4 × 146                                                                          -19, ΔH.sub.r.sup.0 (298 K.) = -603 kJ                                   mol.sup.-1,                                                  [II-211]                                                                           SnO(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.4 Sn(g)                        + CH.sub.3).sub.2 O(g)                                                     -286     6 × 146                                                                        -19 -184, ΔH.sub.r.sup.0 (298 K.) =  -793 kJ                                 mol.sup.-1                                                  [II-212]                                                                           SnO.sub.2 (cr) + 8CH.sub.3 (g) → (CH.sub.3).sub.4 Sn(g) +               2(CH.sub.3).sub.2 O(g)                                                     -581     8 × 146                                                                       -19 2 × -184, ΔH.sub.r.sup.0 (298 K.) = -974 kJ                        mol.sup.-1,                                                  [II-213]                                                                           Sn(cr) + 4H(g) → SnH.sub.4 (g)                                      0         4 × 218                                                                          163, ΔH.sub.r.sup.0 (298 K.) = -709 kJ                                   mol.sup.-1                                                   0         4 × 203                                                                          188, ΔG.sub.r.sup.0 (298 K.) = -624 kJ                                   mol.sup.-1,                                                  [II-214]                                                                           SnO(cr) + 6H(g) → SnH.sub.4 (g) + H.sub.2 O(g)                      -286     6 × 218                                                                        163 -242, ΔH.sub.r.sup.0 (298 K.) = -1101 kJ                                 mol.sup.-1                                                  -257     6 × 203                                                                        188 -229, ΔG.sub.r.sup.0 (298 K.) = -1002 kJ                                 mol.sup.-1                                                  and                                                                            [II-215]                                                                           SnO.sub.2 (cr) + 8H(g) → SnH.sub.4 (g) + 2H.sub.2 O(g)              -581    8 × 218                                                                       163                                                                               2 × -242, ΔH.sub.r.sup.0 (298 K.) = -1481 kJ                       mol.sup.-1                                                     -520    8 × 203                                                                       188                                                                               2 × -229, ΔG.sub.r.sup.0 (298 K.) = -1374 kJ                       mol.sup.-1.                                                    __________________________________________________________________________

Both SnF₂ and SnF₄ are known compounds. In the absence of thermodynamic data on them, however, we can make no comments regarding the efficacy of monofluorine as a volatilizing reagent for tin species. Both methyl and monohydrogen are effective reagents.

    __________________________________________________________________________     [II-216]                                                                           Pb(cr) + O(g) → PbO(cr)                                             0       249      -217,                                                                               ΔH.sub.r.sup.0 (298 K.) = -466 kJ mol.sup.-1       0       232      -188,                                                                               ΔG.sub.r.sup.0 (298 K.) = -420 kJ                                        mol.sup.-1,                                              [II-217]                                                                           PbO(cr) + O(g) → PbO.sub.2 (cr)                                     -217    249      -277,                                                                               ΔH.sub.r.sup.0 (298 K.) = -309 kJ mol.sup.-1       -188    232      -217,                                                                               ΔG.sub.r.sup.0 (298 K.) = -261 kJ                                        mol.sup.-1,                                              [II-218]                                                                           PbF.sub.2 (cr) + 5O(g) → PbO(cr) + 2FO.sub.2 (g)                    -664    5 × 249                                                                       -217                                                                               2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -772 kJ mol.sup.-1       -617    5 × 232                                                                       -188                                                                               2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -677 kJ                                        mol.sup.-1,                                              [II-218]                                                                           PbF.sub.2 (cr) +  6O(g) → PbO.sub.2 (cr) + 2FO.sub.2 (g)            -664    6 × 249                                                                       -277                                                                               2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1081 kJ                                       mol.sup.-1                                               -617    6 × 232                                                                       -217                                                                               2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -938 kJ                                        mol.sup.-1,                                              [II-219]                                                                           PbF.sub.4 (cr) + 9O(g) → PbO(cr) + 4FO.sub.2 (g)                    -942    9 × 249                                                                       -217                                                                               4 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1464 kJ                                       mol.sup.-1,                                              [II-220]                                                                           PbF.sub.4 (cr) + 10O(g) → PbO.sub.2 (cr) + 4FO.sub.2 (g)            -942    10 × 249                                                                      -277                                                                               4 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1773 kJ                                       mol.sup.-1,                                              [II-221]                                                                           Pb(cr) + 2F(g) → PbF.sub.2 (cr)                                     0       2 × 79                                                                            -664,                                                                               ΔH.sub. r.sup.0 (298 K.) = -822 kJ                                       mol.sup.-1                                               0       2 × 62                                                                            -617,                                                                               ΔG.sub.r.sup.0 (298 K.) = -741 kJ                                        mol.sup.-1,                                              [II-222]                                                                           PbF.sub.2 (cr) + 2F(g) → PbF.sub.4 (cr)                             -664    2 × 79                                                                            -942,                                                                               ΔH.sub.r.sup.0 (298 K.) = -436 kJ                                        mol.sup.-1,                                              [II-223]                                                                           PbO(cr) + 4F(g) → PbF.sub.2 (cr) + F.sub.2 O(g)                     -217    4 × 79                                                                        -664                                                                               24,  ΔH.sub.r.sup.0 (298 K.) = -739 kJ mol.sup.-1       -188    4 × 62                                                                        -617                                                                               42,  ΔG.sub.r.sup.0 (298 K.) = -635 kJ                                        mol.sup.-1,                                              [II-224]                                                                           PbO(cr) + 6F(g) → PbF.sub.4 (cr) + F.sub.2 O(g)                     -217    6 × 79                                                                        -942                                                                               24,  ΔH.sub.r.sup.0 (298 K.) = -1175 kJ                                       mol.sup.-1,                                              [II-225]                                                                           PbO.sub.2 (cr) + 6F(g) → PbF.sub.2 (cr) + 2F.sub.2 O(g)             -277    6 × 79                                                                        -664                                                                               2 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -813 kJ mol.sup.-1       -217    6 × 62                                                                        -617                                                                               2 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -688 kJ                                        mol.sup.-1,                                              [II-226]                                                                           PbO.sub.2 (cr) + 8F(g) → PbF.sub.4 (cr) + 2F.sub.2 O(g)             -277    8 × 79                                                                        -942                                                                               2 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1249 kJ                                       mol.sup.-1,                                              [II-227]                                                                           Pb(cr) + 4CH.sub.3 (g) → (CH.sub.3).sub.4 Pb(g)                     0       × 146                                                                             136, ΔH.sub.r.sup.0 (298 K.) = -448 kJ                                        mol.sup.-1,                                              [II-228]                                                                           PbO(cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.4 Pb(g)                        + (CH.sub.3).sub.2 O(g)                                                    -217    6 × 146                                                                       136 -184,                                                                               ΔH.sub.r.sup.0 (298 K.) = -707 kJ                                        mol.sup.-1,                                              [II-229]                                                                           PbO.sub.2 (cr) + 8CH.sub.3 (g) → (CH.sub.3).sub.4 Pb(g) +               2(CH.sub.3).sub.2 O(g)                                                     -277    8 × 146                                                                       136 2 ×                                                                           ΔH.sub.r.sup.0 (298 K.) = -1123 kJ                                       mol.sup.-1,                                                               -184,                                                         [II-230]                                                                           PbF.sub.2 (cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.4 Pb(g) +               2CH.sub.3 F(g)                                                             -664    6 × 146                                                                       136 2 ×                                                                           ΔH.sub.r.sup.0 (298 K.) = 544 kJ mol.sup.-1,                        -284,                                                         and                                                                            [II-231]                                                                           PbF.sub.4 (cr) + 8CH.sub.3 (g) → (CH.sub.3).sub.4 Pb(g) +               4CH.sub.3 F(g)                                                             -942    8 × 146                                                                       136 3 ×                                                                           ΔH.sub.r.sup.0 (298 K.) = -1026 kJ mol.sup.-                             1.                                                                        -234,                                                         __________________________________________________________________________

Thus, we find that methyl is effective for the volatilization of all of the lead compounds discussed here.

F. Group V A.

1. INTRODUCTION

Much of the chemistry of the GROUP VA. elements has been discussed in SECTION IX.D. (GROUP IIIA.). For the convenience of the reader all of the pertinent chemistries except for those of nitrogen will be discussed here.

2. PHOSPHOROUS

    __________________________________________________________________________     [II-232]                                                                           P(cr) + O(g) → PO(g)                                                0       249  -24,       ΔH.sub.r.sup.0 (298 K.) = -273 kJ                                        mol.sup.-1                                             0       232  -47,       ΔG.sub.r.sup.0 (298 K.) = -279 kJ                                        mol.sup.-1,                                            [II-233]                                                                           P(cr) + 1.5O(g) → 0.25P.sub.4 O.sub.6 (g)                           0       1.5 ×                                                                         0.25 × -2214,                                                                       ΔH.sub.r.sup.0 (298 K.) = -927 kJ                                        mol.sup.-1                                                     249                                                                    0       1.5 ×                                                                         0.25 × -2085,                                                                       ΔG.sub.r.sup.0 (298 K.) = -869 kJ                                        mol.sup.-1,                                                    232                                                                    [II-234]                                                                           P(cr) + 2O(g) → PO.sub.2 (g)                                        0       2 × 249                                                                       -315,      ΔH.sub.r.sup.0 (298 K.) = -813 kJ                                        mol.sup.-1                                             0       2 × 232                                                                       -317,      ΔG.sub.r.sup.0 (298 K.) = -781 kJ                                        mol.sup.-1,                                            [II-235]                                                                           P(cr) + 2.5O(g) → 0.25P.sub. 4 O.sub.10 (g)                         0       2.5 ×                                                                         0.25 × -3010,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1375 kJ                                       mol.sup.-1                                                     249                                                                    0       2.5 × 232                                                                     0.25 × -2723,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1261 kJ                                       mol.sup.-1,                                            [II-236]                                                                           P(cr) + 3F(g) → PF.sub.3 (g)                                        0       3 × 79                                                                        -958,      ΔH.sub.r.sup.0 (298 K.) = -1195 kJ                                       mol.sup.-1                                             0       3 × 62                                                                        -937,      ΔG.sub.r.sup.0 (298 K.) = -1123 kJ                                       mol.sup.-1,                                            and                                                                            [II-237]                                                                           P.sub.4 O.sub.10 (cr) + 32F(g) → 4PF.sub.3 (g) + 10F.sub.2              O(g)                                                                       -3010   32 × 79                                                                       4 × -958 10 × 24,                                                             ΔH.sub.r.sup.0 (298 K.) = -3110 kJ                                       mol.sup.-1                                             -2723   32 × 62                                                                       4 × -937, 10 × 42,                                                            ΔG.sub.r.sup.0 (298 K.) =  -2549 kJ                                      mol.sup.-1.                                            __________________________________________________________________________

The `times four` criterion for P₄ O₁₀ is 424 kJ mol⁻¹. Thus, the P₄ O₁₀ generated by [II-235] will vaporize. By [II-237] monofluorine will remove any of the compound present which is not generated by [II-235].

    __________________________________________________________________________     [II-238]                                                                           P(cr) + 3CH.sub.3 (g) → (CH.sub.3).sub.3 P(g)                       0       3 × 146                                                                       -101,        ΔH.sub.r.sup.0 (298 K.) = -539 kJ                                        mol.sup.-1                                           and                                                                            [II-239]                                                                           P.sub.4 O.sub.10 (cr) + 32CH.sub.3 (g) → 4(CH.sub.3).sub.3              P(g) + 10(CH.sub.3).sub.2 O(g)                                             -3010   32 × 146                                                                      4 × -101                                                                       10 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3906 kJ                                       mol.sup.-1                                           __________________________________________________________________________

Thus, methyl as well as monofluorine is an effective reagent for the removal of phosphorous species.

    __________________________________________________________________________     [II-240]                                                                           P(cr) + H(g) → PH(g)                                                0       218  254,       ΔH.sub.r.sup.0 (298 K.) = +36 kJ                                         mol.sup.-1                                             0       203  227,       ΔG.sub.r.sup.0 (298 K.) = +24 kJ                                         mol.sup.-1,                                            [II-241]                                                                           P(cr) + 2H(g) → PH.sub.2 (g)                                        0       2 × 218                                                                       126,       ΔH.sub.r.sup.0 (298 K.) = -310 kJ                                        mol.sup.-1                                             0       2 × 203                                                                       121,       ΔG.sub.r.sup.0 (298 K.) = -285 kJ                                        mol.sup.-1,                                            [II-242]                                                                           P(cr) + 3H(g) → PH.sub.3 (g)                                        0       3 × 218                                                                       23,        ΔH.sub.r.sup.0 (298 K.) = -631 kJ                                        mol.sup.-1                                             0       3 × 203                                                                       31,        ΔG.sub.r.sup.0 (298 K.) = -578 kJ                                        mol.sup.-1                                             and                                                                            [II-243]                                                                           P.sub.4 O.sub.10 (cr) + 32H(g) → 4PH.sub.3 (g) + 10H.sub.2              O(g)                                                                       -3010    32 × 218                                                                     4 × 23                                                                       10 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -6294 kJ                                       mol.sup.-1                                             -2723   32 × 203                                                                      4 × 31                                                                       10 × -229,                                                                      ΔG.sub.r.sup.0 (298 K.) = -5939 kJ                                       mol.sup.-1.                                            __________________________________________________________________________

Thus, should it not be desirable to use either monofluorine or methyl, monohydrogen is quite effective in removing phosphorous species.

3. ARSENIC

Except for AsO the oxides of arsenic are not expected to be volatile in the Apparatus. The trifluoride is volatile, and the pentafluoride (for which we have no thermodynamic data) is a gas.

    __________________________________________________________________________     [II-244]                                                                           As(cr) + O(g) → AsO(g)                                              0       249   70,            ΔH.sub.r.sup.0 (298 K.) = -179 kJ                                        mol.sup.-1,                                       [II-245]                                                                           As(cr) + 1.5O(g) → 0.25As.sub.4 O.sub.6 (cr)                        0       1.5 × 249                                                                      0.25 × -1314,                                                                           ΔH.sub.r.sup.0 (298 K.) = -702 kJ                                        mol.sup.-1                                        0       1.5 × 232                                                                      0.25 × -1152,                                                                           ΔG.sub.r.sup.0 (298 K.) = -636 kJ                                        mol.sup.-1,                                       [II-246]                                                                           As(cr) + 2O(g) → 0.5 As.sub.2 O.sub.4 (cr)                          0       2 × 249                                                                        0.5 × -794,                                                                             ΔH.sub.r.sup.0 (298 K.) = -895 kJ                                        mol.sup.-1,                                       [II-247]                                                                           As(cr) + 2.5O(g) → 0.5As.sub.2 O.sub.5 (cr)                         0       2.5 × 249                                                                      0.5 × -925,                                                                             ΔH.sub.r.sup.0 (298 K.) = -1085 kJ                                       mol.sup.-1,                                       [II-248]                                                                           As(cr) + 3F(g) → AsF.sub.3 (g)                                      0       3 × 79                                                                         -786,          ΔH.sub.r.sup.0 (298 K.) = -1023 kJ                                       mol.sup.-1                                        0       3 × 62                                                                         -771,          ΔG.sub.r.sup.0 (298 K.) = -957 kJ                                        mol.sup.-1,                                       [II-249]                                                                           As.sub.4 O.sub.6 (cr) + 24F(g) → 4AsF.sub.3 (g) + 6F.sub.2              O(g)                                                                       -1314   24 × 79                                                                        4 × -786                                                                       6 × 24,                                                                           ΔH.sub.r.sup.0 (298 K.) = -3582 kJ                                       mol.sup.-1                                        -1152   24 × 62                                                                        4 × -771                                                                       6 × 42,                                                                           ΔG.sub.r.sup.0 (298 K.) = -3168 kJ                                       mol.sup.-1,                                       [II-250]                                                                           As.sub.2 O.sub.4 (cr) + 14F(g) → 2AsF.sub.3 (g) + 4F.sub.2              O(g)                                                                       -794    14 × 79                                                                        2 × -786                                                                       4 × 24,                                                                           ΔH.sub.r.sup.0 (298 K.) = -1788 kJ                                       mol.sup. -1                                       and                                                                            [II-251]                                                                           As.sub.2 O.sub.5 (cr) + 16F(g) → 2AsF.sub.3 (g) + 5F.sub.2              O(g)                                                                       -925    16 × 79                                                                       2 × -786                                                                        5 × 24,                                                                           ΔH.sub.r.sup.0 (298 K.) = -1791 kJ                                       mol.sup.-1.                                       __________________________________________________________________________

Thus, monofluorine is effective in removing all of the oxides of arsenic as well as arsenic itself.

    __________________________________________________________________________     [II-252]                                                                           As(cr) + 3CH.sub.3 (g) → (CH.sub.3).sub.3 As(g)                     0       3 × 146                                                                           13,   ΔH.sub.r.sup.0 (298 K.) = -425 kJ                                        mol.sup.-1,                                             [II-253]                                                                           As.sub.4 O.sub.6 (cr) + 24CH.sub.3 (g) → 4(CH.sub.3).sub.3              As(g) + 6(CH.sub.3).sub.2 O(g)                                             -1314   24 × 146                                                                      4 × 13                                                                       6 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3242 kJ                                       mol.sup.-1,                                             [II-254]                                                                           As.sub.2 O.sub.4 (cr) + 14CH.sub.3 (g) → 2(CH.sub.3).sub.3              As(g) + 4(CH.sub.3).sub.2 O(g)                                             -794    14 × 146                                                                      2 × 13                                                                       4 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1960 kJ                                       mol.sup.-1,                                             [II-255]                                                                           As.sub.2 O.sub.5 (cr) + 16CH.sub.3 (g) → 2(CH.sub.3).sub.3              As(g) + 5(CH.sub.3 ).sub.2 O(g)                                            -925    16 × 146                                                                      2 × 13                                                                       5 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2305 kJ                                       mol.sup.-1,                                             [II-256]                                                                           As(cr) + 3H(g) → AsH.sub.3 (g)                                      0       3 × 218                                                                           66,   ΔH.sub.r.sup.0 (298 K.) = -588 kJ                                        mol.sup.-1                                              0       3 × 203                                                                           69,   ΔG.sub.r.sup.0 (298 K.) = 540 kJ                                         mol.sup.-1,                                             [II-257]                                                                           As.sub.4 O.sub.6 (cr) + 24H(g) → 4AsH.sub.3 (g) + 6H.sub.2              O(g)                                                                       -1314   24 × 218                                                                      4 × 66                                                                       6 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -5106 kJ                                       mol.sup.-1                                              -1152   24 × 203                                                                      4 × 69                                                                       6 × -229,                                                                      ΔG.sub.r.sup.0 (298 K.) = -4818 kJ                                       mol.sup.-1,                                             [II-258]                                                                           As.sub.2 O.sub.4 (cr) + 14H(g) → 2AsH.sub.3 (g) + 4H.sub.2              O(g)                                                                       -794    14 × 218                                                                      2 × 66                                                                       4 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3094 kJ                                       mol.sup.-1                                              and                                                                            [II-259]                                                                           As.sub.2 O.sub.5 (cr) + 16H(g) → 2AsH.sub.3 (g) + 5H.sub.2              O(g)                                                                       -925    16 × 218                                                                      2 × 66                                                                       5 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3641 kJ                                       mol.sup.-1.                                             __________________________________________________________________________

Thus, both methyl and monohydrogen are effective in removing all of the oxides of arsenic as well as arsenic itself.

4. ANTIMONY

    __________________________________________________________________________     [II-260]                                                                           Sb(cr) + O(g) → SbO(g)                                              0       249   199,           ΔH.sub.r.sup.0 (298 K.) = -50 kJ                                         mol.sup.-1,                                       [II-261]                                                                           Sb(cr) + 1.5O(g) → 0.25Sb.sub.4 O.sub.6 (g)                         0       1.5 × 249                                                                      0.25 × -1441,                                                                           ΔH.sub.r.sup.0 (298 K.) = -734 kJ                                        mol.sup.-1                                        0       1.5 × 232                                                                      0.25 × -1268,                                                                           ΔG.sub.r.sup.0 (298 K.) = -665 kJ                                        mol.sup.-1,                                       [II-262]                                                                           Sb(cr) + 2O(g) → 0.5Sb.sub.2 O.sub.4 (cr)                           0       2 × 249                                                                        0.5 × -908,                                                                             ΔH.sub.r.sup.0 (298 K.) = -952 kJ                                        mol.sup.-1                                        0       2 × 232                                                                        0.5 × -796,                                                                             ΔG.sub.r.sup.0 (298 K.) = -862 kJ                                        mol.sup.-1,                                       [II-263]                                                                           Sb(cr) + 2.5O(g) → 0.5Sb.sub.2 O.sub.5 (cr)                         0       2.5 × 249                                                                      0.5 × -972,                                                                             ΔH.sub.r.sup.0 (298 K.) = -1108 kJ                                       mol.sup.-1                                        0       2.5 × 232                                                                      0.5 × -829,                                                                             ΔG.sub.r.sup.0 (298 K.) = -974 kJ                                        mol.sup.-1,                                       [II-264]                                                                           Sb(cr) + F(g) → SbF(g)                                              0       79    -47,           ΔH.sub.r.sup.0 (298 K.) = -126 kJ                                        mol.sup.-1,                                       [II-265]                                                                           Sb(cr) + 3F(g) → SbF.sub.3 (cr)                                     0       3 × 79                                                                         -916,          ΔH.sub.r.sup.0 (298 K.) = -1153 kJ                                       mol.sup.-1,                                       [II-266]                                                                           Sb.sub.4 O.sub.6 (cr) + 24F(g) → 4SbF.sub.3 (cr) + 6F.sub.2             O(g)                                                                       -1441   24 × 79                                                                        4 × -916                                                                        6 × 24,                                                                          ΔH.sub.r.sup.0 (298 K.) = -3975 kJ                                       mol.sup.-1,                                       [II-267]                                                                           Sb.sub.2 O.sub.4 (cr) + 14F(g) → 2SbF.sub.3 (cr) + 4F.sub.2             O(g)                                                                       -908    14 × 79                                                                        2 × -916                                                                        4 × 24,                                                                          ΔH.sub.r.sup.0 (298 K.) = -1934 kJ                                       mol.sup.-1,                                       and                                                                            [II-268]                                                                           Sb.sub.2 O.sub.5 (cr) + 16F(g) → 2SbF.sub.3 (cr) + 5F.sub.2             O(g)                                                                       -972    16 × 79                                                                        2 × -916                                                                        5 × 24,                                                                          ΔH.sub.r.sup.0 (298 K.) = -2004 kJ                                       mol.sup.-1.                                       __________________________________________________________________________

The enthalpy of sublimation of antimony trifluoride is 869 kJ mol⁻¹, making the `times four` criterion 3476 kJ mol⁻¹. Thus, monofluorine is not an effective reagent for removing antimony species. (It should be noted that the enthalpy of reaction for [II-266] is for 4 antimony trifluorides.)

    __________________________________________________________________________     [II-269]                                                                           Sb(cr) + 3CH.sub.3 (g) → (CH.sub.3).sub.3 Sb(g)                     0       3 × 146                                                                       +32,       ΔH.sub.r.sup.0 (298 K.) = -406 kJ                                        mol.sup.-1,                                            [II-270]                                                                           Sb.sub.4 O.sub.6 (cr) + 24CH.sub.3 (g) → 4(CH.sub.3).sub.3              Sb(g) + 6(CH.sub.3).sub.2 O(g)                                             -1441   24 × 146                                                                      4 × 32                                                                        6 × 184,                                                                       ΔH.sub.r.sup.0 (298 K.) = -3039 kJ                                       mol.sup.-1,                                            [II-271]                                                                           Sb.sub.2 O.sub.4 (cr) + 14CH.sub.3 (g) → 2(CH.sub.3).sub.3              Sb(g) + 4(CH.sub.3).sub.2 O(g)                                             -908    14 × 146                                                                      2 × 32                                                                        4 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1808 kJ                                       mol.sup.-1,                                            [II-272]                                                                           Sb.sub.2 O.sub.5 (cr) + 16CH.sub.3 (g) → 2(CH.sub.3).sub.3              Sb(g) + 5(CH.sub.3 ).sub.2 O(g)                                            -972    16 × 146                                                                      2 × 32                                                                        5 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2220 kJ                                       mol.sup.-1,                                            [II-273]                                                                           SbF.sub.3 (cr) + 4CH.sub.3 (g) → (CH.sub.3).sub.3 Sb(g) +               3CH.sub.3 F(g)                                                             -916    4 × 146                                                                       32   3 × -234,                                                                      ΔH.sub.r.sup.0 (298 K.) = -338 kJ                                        mol.sup.-1,                                            [II-274]                                                                           Sb(cr) + 3H(g) → SbH.sub.3 (g)                                      0       3 × 218                                                                       145,       ΔH.sub.r.sup.0 (298 K.) = -509 kJ                                        mol.sup.-1                                             0       3 × 203                                                                       148,       ΔG.sub.r.sup.0 (298 K.) = -461 kJ                                        mol.sup.-1,                                            [II-275]                                                                           Sb.sub.4 O.sub.6 (cr) + 24H(g) → 4SbH.sub.3 (g) + 6H.sub.2              O(g)                                                                       -1441   24 × 218                                                                      4 × 145                                                                       6 × -242,                                                                      ΔH.sub.r.sup. 0 (298 K.) = -4663 kJ                                      mol.sup.-1                                             -1268   24 × 203                                                                      4 × 148                                                                       6 × -229,                                                                      ΔG.sub.r.sup.0 (298 K.) = 4386 kJ                                        mol.sup.-1,                                            [II-276]                                                                           Sb.sub.2 O.sub.4 (cr) + 14H(g) → 2SbH.sub.3 (g) + 4H.sub.2              O(g)                                                                       -908    14 × 18                                                                       2 × 145                                                                       4 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2822 kJ                                       mol.sup.-1                                             -796    14 × 203                                                                      2 × 148                                                                       4 × -229,                                                                      ΔG.sub.r.sup.0 (298 K.) = -2666 kJ                                       mol.sup.-1,                                            [II-277]                                                                           Sb.sub.2 O.sub.5 (cr) + 16H(g) → 2SbH.sub.3 (g) + 5H.sub.2              O(g)                                                                       -972    16 × 218                                                                      2 × 145                                                                       5 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3436 kJ                                       mol.sup.-1                                             -829    16 × 203                                                                      2 × 148                                                                       5 × -229,                                                                      Δ G.sub.r.sup.0 (298 K.) = -3268 kJ                                      mol.sup.-1                                             and                                                                            [II-278]                                                                           SbF.sub.3 (cr) + 6H(g) → SbH.sub.3 (g) + 3HF(g)                     -916    6 × 218                                                                       145  4 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1063 kJ                                       mol.sup.-1.                                            __________________________________________________________________________

Thus, both methyl and monohydrogen are effective reagents for the removal of all of the antimony species discussed here.

5. BISMUTH

    __________________________________________________________________________     [II-279]                                                                           Bi(cr) + 1.5O(g) → 0.5Bi.sub.2 O.sub.3 (cr)                         0       1.5 × 249                                                                      0.5 × -574,                                                                            ΔH.sub.r.sup.0 (298 K.) = -660 kJ                                        mol.sup.-1                                         0       1.5 × 232                                                                      0.5 × -494,                                                                            ΔG.sub.r.sup.0 (298 K.) = -595 kJ                                        mol.sup.-1,                                        [II-280]                                                                           BiCl.sub.3 (cr) + 7.5O(g) → 0.5Bi.sub.2 O(cr) + 3ClO.sub.2              (g)                                                                        -379    7.5 × 249                                                                      0.5 × -574                                                                      3 × 102,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1470 kJ                                       mol.sup.-1,                                        -315    7.5 × 232                                                                      0.5 × -494                                                                      3 × 120,                                                                        ΔG.sub.r.sup.0 (298 K.) = -1312 kJ                                       mol.sup.-1,                                        [II-281]                                                                           BiF.sub.3 (cr) + 7.5O(g) → 0.5Bi.sub.2 O.sub.3 (cr)                     + 3FO.sub.2 (g)                                                            -904    7.5 × 249                                                                      0.5 × -574                                                                      3 ×  13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1212 kJ                                       mol.sup.-1                                         -940    7.5 × 232                                                                      0.5 × -494                                                                      3 × 27,                                                                         ΔG.sub.r.sup.0 (298 K.) = -966 kJ                                        mol.sup.-1,                                        [II-282]                                                                           Bi(cr) + 3CH.sub.3 (g) → (CH.sub.3).sub.3 Bi(g)                     0       3 × 146                                                                        194,          ΔH.sub.r.sup.0 (298 K.) = -244 kJ                                        mol.sup.-1,                                        [II-283]                                                                           Bi.sub.2 O.sub.3 (cr) + 12CH.sub.3 (g) → 2(CH.sub.3).sub.3              Bi(g) + 3(CH.sub.3).sub.2 O(g)                                             -574    12 × 146                                                                       2 × 194                                                                         3 × -184,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1342 kJ                                       mol.sup.-1,                                        [II-284]                                                                           BiCl.sub.3 (cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Bi(g) +              CH.sub.3 Cl(g)                                                             -379    6 × 146                                                                        194    3 × -84,                                                                        Δ H.sub.r.sup.0 (298 K.) = -555 kJ                                       mol.sup.-1                                         and                                                                            [ II-285]                                                                          BiF.sub.3 (cr) + 6CH.sub.3 (g) → (CH.sub.3).sub.3 Bi(g) +               3CH.sub.3 F(g)                                                             -904    6 × 146                                                                        194    3 × -234,                                                                       ΔH.sub.r.sup.0 (298 K.) = -480 kJ                                        mol.sup.-1.                                        __________________________________________________________________________

Thus, methyl is an effective reagent for the removal of all of the bismuth species discussed here.

G. Group VI A.

1. THERMODYNAMICS

                  TABLE II-7                                                       ______________________________________                                         GROUP VIA                                                                      THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES S            Se          Te                                            ______________________________________                                         MO   (g)    +5/-24       +53.sup.a /+27.sup.a                                                                     +65.sup.a /+38.sup.a                        MO.sub.2                                                                            (cr)                -225.sup.a /--                                                                           -323.sup.a /-270.sup.a                           (g)    -297/-300                                                          MO.sub.3                                                                            (cr)   -455.sup.a /-374.sup.a                                                                      -167.sup.a /--                                             (l)    -441.sup.a /-374.sup.a                                                  (g)    -396/-371                                                          MF   (g)    +13/-14                                                            MF.sub.2                                                                            (g)    -297/-303                                                          MF.sub.3                                                                            (g)    -503/-488                                                          MF.sub.4                                                                            (g)    -763/-722                                                          MF.sub.5                                                                            (g)    -908/-839                                                          MF.sub.6                                                                            (g)    -1220/-1116  -1117.sup.a /-1017.sup.a                                                                 -1318.sup.a /--                             HM   (g)    +139/+105                                                          H.sub.2 M                                                                           (g)    -28/-40      +30.sup.a /+16.sup.a                                                                     +100.sup.a /--                              ______________________________________                                          (.sup.a Ref. <B>).                                                       

2. SULFUR

By the criterion of [II-1] sulfur trioxide will vaporize spontaneously in the Apparatus. Thus, the only solid species of sulfur which will be considered here is sulfur itself.

    __________________________________________________________________________     [II-286]                                                                           S(cr) + O(g) → SO(g)                                                0      249   5,   ΔH.sub.r.sup.0 (298 K.) = -244 kJ mol.sup.-1           0      232   -21, ΔG.sub.r.sup.0 (298 K.) = -253 kJ mol.sup.-1,          [II-287]                                                                           S(cr) + 2O(g) → SO.sub.2 (g)                                        0      2 × 249                                                                        -297,                                                                               ΔH.sub.r.sup.0 (298 K.) = -795 kJ mol.sup.-1           0      2 × 232                                                                        -300,                                                                               ΔG.sub.r.sup.0 (298 K.) = -764 kJ mol.sup.-1,          [II-288]                                                                           S(cr) + 3O(g) → SO.sub.3 (g)                                        0      3 × 249                                                                        -396,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1143 kJ mol.sup.-1          0      3 × 232                                                                        -371,                                                                               ΔG.sub.r.sup.0 (298 K.) = -1067 kJ mol.sup.-1,         [II-289]                                                                           S(cr) + F(g) → SF(g)                                                0      79    +13, ΔH.sub.r.sup. 0 (298 K.) = -66 kJ mol.sup.-1           0      62    -14, ΔG.sub.r.sup.0 (298 K.) = -76 kJ mol.sup.-1,           [II-290]                                                                           S(cr) + 2F(g) → SF.sub.2 (g)                                        0      2 × 79                                                                         -297,                                                                               ΔH.sub.r.sup.0 (298 K.) = -455 kJ mol.sup.-1           0      2 × 62                                                                         -303,                                                                               ΔG.sub.r.sup.0 (298 K.) = -427 kJ mol.sup.-1,          [II-291]                                                                           S(cr) + 3F(g) → SF.sub.3 (g)                                        0      3 × 79                                                                         -503,                                                                               ΔH.sub.r.sup.0 (298 K.) = -740 kJ mol.sup.-1           0      3 × 62                                                                         -488,                                                                               ΔG.sub.r.sup.0 (298 K.) = -674 kJ mol.sup.-1,          [II-292]                                                                           S(cr) + 4F(g) → SF.sub.4 (g)                                        0      4 × 79                                                                         -763,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1079 kJ mol.sup.-1          0      4 × 62                                                                         -722,                                                                               ΔG.sub. r.sup.0 (298 K.) = -970 kJ mol.sup.-1,         [II-293]                                                                           S(cr) + 5F(g) → SF.sub.5 (g)                                        0      5 × 79                                                                         -908,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1303 kJ mol.sup.-1          0      5 × 62                                                                         -839,                                                                               ΔG.sub.r.sup.0 (298 K.) = -1149 kJ mol.sup.-1,         [II-294]                                                                           S(cr) + 6F(g) → SF.sub.6 (g)                                        0      6 × 79                                                                         -1220,                                                                              ΔH.sub.r.sup.0 (298 K.) = -1694 kJ mol.sup.-1          0      6 × 62                                                                         -1116,                                                                              ΔG.sub.r.sup.0 (298 K.) = -1488 kJ mol.sup.-1,         [II-295]                                                                           S(cr) + 2CH.sub.3 (g) → (CH.sub.3).sub.2 S(g)                       0      2 × 146                                                                        -37, ΔH.sub.r.sup.0 (298 K.) = -329 kJ mol.sup.-1,          [II-296]                                                                           S(cr) + H(g) → HS(g)                                                0      218   139, ΔH.sub. r.sup.0 (298 K.) = -79 kJ mol.sup.-1           0      203   105, ΔG.sub.r.sup.0 (298 K.) = -98 kJ mol.sup.-1            and                                                                            [II-297]                                                                           S(cr) + 2H(g) → H.sub.2 S(g)                                        0      2 × 218                                                                        -28, ΔH.sub.r.sup.0 (298 K.) = -464 kJ mol.sup.-1           0      2 × 203                                                                        -40, ΔG.sub.r.sup.0 (298 K.) = -446 kJ                      __________________________________________________________________________                       mol.sup.-1.                                             

Thus, monoxygen, monofluorine, methyl and monohydrogen are all effective volatilizing reagents.

3. SELENIUM

    __________________________________________________________________________     [II-298]                                                                           Se(cr) + O(g) → SeO(g)                                              0       249  53,       ΔH.sub.r.sup.0 (298 K.) = -196 kJ                                        mol.sup.-1                                              0       232  27,       ΔG.sub.r.sup.0 (298 K.) = -205 kJ                                        mol.sup.-1,                                             [II-299]                                                                           Se(cr) + 2O(g) → SeO.sub.2 (cr)                                     0       2 × 249                                                                       -225,     ΔH.sub.r.sup.0 (298 K.) = -723 kJ                                        mol.sup.-1,                                             [II-300]                                                                           Se(cr) + 3O(g) → SeO.sub.3 (cr)                                     0       3 × 249                                                                       -167,     ΔH.sub.r.sup.0 (298 K.) = -914 kJ                                        mol.sup.-1,                                             [II-301]                                                                           Se(cr) + 6F(g) → SeF.sub.6 (g)                                      0       6 × 79                                                                        -1117,    ΔH.sub.r.sup.0 (298 K.) = -1591 kJ                                       mol.sup.-1                                              0       6 × 62                                                                        -1017,    ΔG.sub.4.sup.0 (298 K.) = -1389 kJ                                       mol.sup.-1,                                             [II-302]                                                                            SeO.sub.2 (cr) + 10F(g) → SeF.sub.6 (g) + 2F.sub.2 O(g)            -225    10 × 79                                                                       -1117                                                                              2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1634 kJ                                       mol.sup.-1,                                             [II-303]                                                                           SeO.sub.3 (cr) + 12F(g) → SeF.sub.6 (g) + 3F.sub.2 O(g)             -167    12 × 79                                                                       -1117                                                                              3 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1826 kJ                                       mol.sup.-1,                                             [II-304]                                                                           Se(cr) + 2H(g) → H.sub.2 Se(g)                                      0       2 × 218                                                                       30,       ΔH.sub.r.sup.0 (298 K.) = -406 kJ                                        mol.sup.-1                                              0       2 × 203                                                                       16,       ΔG.sub.r.sup.0 (298 K.) = -390 kJ                                        mol.sup.-1,                                             [II-305]                                                                           SeO.sub.2 (cr) + 6H(g) → H.sub.2 Se(g) + 2H.sub.2 O(g)              -225    6 × 218                                                                       30  2 × -242,                                                                      ΔH.sub. r.sup.0 (298 K.) = -1537 kJ                                      mol.sup.-1                                              and                                                                            [II-306]                                                                           SeO.sub.3 (cr) + 8H(g) → H.sub.2 Se(g) + 3H.sub.2 O(g)              -167    8 × 218                                                                       30  3 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2273 kJ                                       mol.sup.-1.                                             __________________________________________________________________________

Thus, both monofluorine and monohydrogen are effective volatilizing reagents. Although methyl is probably an effective reagent also, we cannot confirm this in the absence of thermodynamic data.

4. TELLURIUM

    __________________________________________________________________________     [II-307]                                                                           Te(cr) + O(g) → TeO(g)                                              0       249  65,       ΔH.sub.r.sup.0 (298 K.) = -184 kJ                                        mol.sup.-1                                              0       232  38,       ΔG.sub.r.sup.0 (298 K.) = -194 kJ                                        mol.sup.-1,                                             [II-308]                                                                           Te(cr) + 2O(g) → TeO.sub.2 (cr)                                     0       2 × 249                                                                       -323,     ΔH.sub.r.sup.0 (298 K.) = -821 kJ                                        mol.sup.-1                                              0       2 × 232                                                                       -270,     ΔG.sub.r.sup.0 (298 K.) = -734 kJ                                        mol.sup.-1,                                             [II-309]                                                                           Te(cr) + 6F(g) → TeF.sub.6 (g)                                      0       6 × 79                                                                        -1318,    ΔH.sub.r.sup.0 (298 K.) = -1792 kJ                                       mol.sup.-1,                                             [II-310]                                                                           TeO.sub.2 (cr) + 10F(g) → TeF.sub.6 (g) + 2F.sub.2 O(g)             -323    10 × 79                                                                       -1318                                                                              2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1737 kJ                                       mol.sup.-1,                                             [II-311]                                                                           Te(cr) + 2H(g) → H.sub.2 Te(g)                                      0      2 × 218                                                                        100,      ΔH.sub.r.sup.0 (298 K.) = -336 kJ                                        mol.sup.-1                                              and                                                                            [II-312]                                                                           TeO.sub.2 (cr) + 6H(g) → H.sub.2 Te(g) + 2H.sub.2 O(g)              -323    6 × 218                                                                       100 2× -242,                                                                       ΔH.sub.r.sup.0 (298 K.) =-1369 kJ                 __________________________________________________________________________                            mol.sup.-1.                                        

Thus, both monofluorine and monohydrogen are effective volatilizing reagents. As is the case with selenium, methyl is probably an effective reagent also, but we cannot confirm this in the absence of thermodynamic data.

H. Summary of Main Group elements Chemistries

                  TABLE II-8                                                       ______________________________________                                         SUMMARY OF MAIN GROUP ELEMENTS CHEMISTRIES                                     CHEMISTRY                                                                             O/NO.sub.2 +           O +                                              GROUP  F         O     F      CH.sub.3                                                                            CH.sub.3                                                                            H                                      ______________________________________                                         IA     ALL                                                                     IIA    ALL                                                                     IIIA   B, Al(?)        B, Al(?)                                                                              ALL  ALL                                         IVA    C, Si, Ge C     C, Si, Ge                                                                             ALL  ALL  C, Si, Ge, Sn                          VA     P, As           P, As  ALL  ALL  P, As, Sb                              VIA    ALL       S     ALL    S    S    ALL                                    ______________________________________                                    

As the data in TABLE II-8 show the schedule O/NO₂ °F+CH₃ will remove all main group element species as well as non-fluorocarbon organics. If a large amount of fluorocarbon is present, such as in the case in which a fluorocarbon mask has been used, the schedule should be changed to H+O/NO₂ +F+CH₃. If only a small amount of fluorocarbon is present, or suspected, the schedule O/NO₂ +F+CH₃ +H can be used. This schedule is preferred if silicon expitaxy, for example, is to be carried out immediately after the cleaning schedule. This is because the `hydrogenated` surface usually leads to a better quality expitaxial layer. Since other chemistries must be added to the schedules for the removal of transition metal species and lanthanide species, we shall now turn to the analysis of the chemistries of these species.

I. Group III B.

1. THERMODYNAMICS

                  TABLE II-9                                                       ______________________________________                                         GROUP IIIB                                                                     THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES      Sc            Y                                                   ______________________________________                                         MO      (g)      -57/-83       -39/-65                                         M.sub.2 O.sub.3                                                                        (cr)     -1909/-1819   -1905/-1817                                     MCl.sub.3                                                                              (cr)     -925/--       -1000/--                                        MF      (g)      -139/-164     -138/-163                                       MF.sub.2                                                                               (g)      -642/-655                                                     MF.sub.3                                                                               (cr)     -1629/-1556   -1719/-1645                                             (g)      -1247/-1234   -1289/-1278                                     MH.sub.2                                                                               (cr)     -192/--       -226/-185                                       MH.sub.3                                                                               (cr)                   -268/-209                                       ______________________________________                                          (all data are from Ref. <B>).                                            

In the absence of any thermodynamic data on the nitrates we can make no definitive statement on the efficacy of the O/NO₂ +F procedure. We shall return to this question after the completion of the analysis of the lanthanide species chemistries.

2SCANDIUM

    __________________________________________________________________________     [II-313]                                                                           Sc(cr) + O(g) → ScO(g)                                              0          249   -57,         ΔH.sub.r.sup.0 (298 K.) = -306 kJ                                        mol.sup.-1                                       0          232   -83,         ΔG.sub.r.sup.0 (298 K.) = -315 kJ                                        mol.sup.-1,                                      [II-314]                                                                           Sc(cr) + 1.5O(g) → 0.5Sc.sub.2 O.sub.3(g)                           0          1.5 × 249                                                                      0.5 × -1909,                                                                          ΔH.sub.r.sup.0 (298 K.) = -1328 kJ                                       mol.sup.-1                                       0          1.5 × 232                                                                      0.5 × -1819,                                                                          ΔG.sub.r.sup.0 (298 K.) = -1258 kJ                                       mol.sup.-1,                                      [II-315]                                                                           ScCl.sub.3 (cr) + 7.5O(g) → 0.5Sc.sub.2 O.sub.3 (cr) +                  3ClO.sub.2 (g)                                                             -925       7.5 × 249                                                                      0.5 × -1909                                                                     3 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1591 kJ                                       mol.sup.-1,                                      [II-316]                                                                           ScF.sub.3 (cr) + 7.5O(g) → 0.5Sc.sub.2 O.sub.3 (cr)                     + 3FO.sub.2 (g)                                                            -1629      7.5 × 249                                                                      0.5 × -1909                                                                     3 × 13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1154 kJ                                       mol.sup.-1                                       -1556      7.5 × 232                                                                      0.5 × -1819                                                                     3 × 27,                                                                        ΔG.sub.r.sup.0 (298 K.) = -1012 kJ                                       mol.sup.-1                                       and                                                                            [II-317]                                                                           ScH.sub.2 (cr) + 2.5O(g) → 0.5Sc.sub.2 O.sub.3 (cr) + H.sub.2           O(g)                                                                       -192       2.5 × 249                                                                      0.5 × -1909                                                                     -242, ΔH.sub.r.sup.0 (298 K.) = -1627 kJ                                       mol.sup.-1.                                      [II-318]                                                                           Sc(cr) + F(g) → ScF(g)                                              0          79    -139,        ΔH.sub.r.sup.0 (298 K.) = -218 kJ                                        mol.sup.-1                                       0          62    -164,        ΔG.sub.r.sup.0 (298 K.) = -226 kJ                                        mol.sup.-1,                                      [II-319]                                                                           Sc(cr) + 2F(g) → ScF.sub.2 (g)                                      0          2 × 79                                                                         -642,        ΔH.sub.r.sup.0 (298 K.) = -800 kJ                                        mol.sup.-1                                       0          2 × 62                                                                         -655,        ΔG.sub.r.sup.0 (298 K.) = -779 kJ                                        mol.sup.-1                                       [II-320]                                                                           Sc(cr) + 3F(g) → ScF.sub.3 (cr)                                     0          3 × 79                                                                         -1629,       ΔH.sub.r.sup.0 (298 K.) = -1866 kJ                                       mol.sup.-1                                       0          3 × 62                                                                         -1556,       ΔG.sub.r.sup.0 (298 K.) = -1742 kJ                                       mol.sup.-1,                                      [II-321]                                                                           0.5Sc.sub.2 O.sub.3 (cr) + 6F(g) → ScF.sub.3 (cr)                       + 1.5OF.sub.2 (g)                                                          0.5 × -1909                                                                         6 × 79                                                                         -1629  1.5 × 24,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1112 kJ                                       mol.sup.-1                                       0.5 × -1819                                                                         6 × 62                                                                         -1556  1.5 × 42,                                                                      ΔG.sub.r.sup.0 (298 K.) = -956 kJ                                        mol.sup.-1,                                      [II-322]                                                                           0.5Sc.sub.2 O.sub.3 (cr) + 6F*(g) → ScF.sub.3 (cr)                      + 1.5OF.sub.2 (g)                                                          0.5 × -1909                                                                         6 × 245                                                                        -1629                                                                              1.5 × 24,                                                                         ΔH.sub.r *(298 K.) = -2108 kJ                                            mol.sup.-1,                                      [II-323]                                                                           ScCl.sub.3 (cr) + 12F(g) → ScF.sub.3 (cr) + 3ClF.sub.3 (g)          -925       12 × 79                                                                        -1629  3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2129 kJ                                       mol.sup.-1                                       and                                                                            [II-324]                                                                           ScH.sub.2 (cr) + 5F(g) → ScF.sub.3 (cr) + 2HF(g)                    -192       5 × 29                                                                         -1629  2 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2376 kJ                                       mol.sup.-1.                                      __________________________________________________________________________

The enthalpy of sublimation of scandium fluoride is 382 kJ mol⁻¹, and the `times four` criterion is 1528 kJ mol⁻¹. Since the monofluorines are not in their ground state (cf. SECTION IX. A.), the criterion is met even for the sesquioxide.

    __________________________________________________________________________     [II-325]                                                                           Sc.sub.2 O.sub.3 (cr) + 10 H(g) →2 ScH.sub.2 (cr) + 3 H.sub.2           O(g)                                                                       -1909   10 × 218                                                                      2 × -196                                                                       3 × -242,                                                                     ΔH.sub.r.sup.0 (298K) = -1381 kJ                                         mol.sup.-1,                                            [II-326]                                                                           ScCl.sub.3L (cr) + 5 H(g) → ScH.sub.2 (cr) + 3 HCl(g)               -925    5 × 218                                                                       -192  3 × 92,                                                                       ΔH.sub.r.sup.0 (298K) = -633 kJ mol.sup.-1       and                                                                            II-327]                                                                            ScF.sub.3 (cr) + 5 H(g) → ScH.sub.2 (cr) + 3 HF(g)                  -1629   5 × 218                                                                       -192  3 × -272,                                                                     ΔH.sub.r.sup.0 (298K) = -469 kJ                  __________________________________________________________________________                             mol.sup.-1.                                       

Thus, for the volatilization of scandium species we have the choice of three procedures:

O+F*

H+F

F* (in the absence of ScF₃).

3. YTTRIUM

The enthalpy of sublimation of yttrium trifluoride is 430 kJ mol⁻¹, and the `times four` criterion is 1720 kJ mol⁻¹.

    __________________________________________________________________________     [II-328]                                                                           Y(cr) + O(g) → YO(g)                                                0          249   -39,          ΔH.sub.r.sup.0 (298 K.) = -288 kJ                                        mol.sup.-1                                      0          232   -65,          ΔG.sub.r.sup.0 (298 K.) = -297 kJ                                        mol.sup.-1,                                     [II-329]                                                                           Y(cr) + 1.5O(g) → 0.5Y.sub.2 O.sub.3 (cr)                           0          1.5 × 249                                                                      0.5 × -1905,                                                                           ΔH.sub.r.sup.0 (298 K.) = -1326 kJ                                       mol.sup.-1                                      0          1.5 × 232                                                                      0.5 × -1817,                                                                           ΔG.sub.r.sup.0 (298 K.) = -1256 kJ                                       mol.sup.-1,                                     [II-330]                                                                           YCl.sub.3 (cr) + 7.5O(g) → Y.sub.2 O.sub.3 (cr) + 3ClO.sub.2            (g)                                                                        -1000      7.5 × 249                                                                      0.5 × -1905                                                                     3 × 102,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1514 kJ                                       mol.sup.-1,                                     [II-331]                                                                           YF.sub.3 (cr) + 7.5O(g) → 0.5Y.sub.2 O.sub.3 (cr) + 3FO.sub.2           (g)                                                                        -1719      7.5 × 249                                                                      0.5 × -1905                                                                     3 × 13,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1062 kJ                                       mol.sup.-1                                      -1645      7.5 × 232                                                                      0.5 × -1817                                                                     3 × 27,                                                                         ΔG.sub.r.sup.0 (298 K.) = -922 kJ                                        mol.sup.-1,                                     [II-332]                                                                           YH.sub.2 (cr) + 2.5O(g) → 0.5Y.sub.2 O.sub.3 (cr) + H.sub.2             O(g)                                                                       -226       2.5 × 249                                                                      0.5 × -1905                                                                     -242,  ΔH.sub.r.sup.0 (298 K.) = -1591 kJ                                       mol.sup.-1                                      -185       2.5 × 232                                                                      0.5 × -1817                                                                     -229,  ΔG.sub.r.sup.0 (298 K.) = -1532 kJ                                       mol.sup.-1,                                     and                                                                            [II-333]                                                                           YH.sub.3 (cr) + 3O(g) → 0.5Y.sub.2 O.sub.3 (cr) + 1.5H.sub.2            O(g)                                                                       -268       3 × 249                                                                        0.5 × -1905                                                                     1.5 × -242,                                                                     Δ H.sub.r.sup.0 (298 K.) = -1794 kJ                                      mol.sup.-1                                      -209       3 × 232                                                                        0.5 × -1819                                                                     1.5 × -229,                                                                     ΔG.sub.r.sup.0 (298 K.) = -1739 kJ                                       mol.sup.-1                                      [II-334]                                                                           Y(cr) + F(g) → YF(g)                                                0          79    -138,         ΔH.sub.r.sup.0 (298 K.) = -217 kJ                                        mol.sup.-1                                      0          62    -163,         ΔG.sub.r.sup.0 (298 K.) = -225 kJ                                        mol.sup.-1,                                     [II-335]                                                                           Y(cr) + 3F(g) → YF.sub.3 (cr)                                       0          3 × 79                                                                         -1719,        ΔH.sub.r.sup.0 (298 K.) = -1956 kJ                                       mol.sup.-1                                      0          3 × 62                                                                         -1645,        ΔG.sub.r.sup.0 (298 K.) = -1831 kJ                                       mol.sup.-1,                                     [II-336]                                                                           0.5Y.sub.2 O.sub.3 (cr) + 6F(g) → YF.sub.3 (cr) + 1.5OF.sub.2           (g)                                                                        0.5 × -1905                                                                         6 × 79                                                                         -1719  1.5 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1204 kJ                                      mol.sup.-1                                      0.5 × 1817                                                                          6 × 62                                                                         -1645  1.5 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1046 kJ                                       mol.sup.-1,                                     [II-337]                                                                           0.5Y.sub.2 O.sub.3 (cr) + 6F*(g) → YF.sub.3 (cr) + 1.5OF.sub.2          (g)                                                                        0.5 × -1905                                                                         6 × 245                                                                        -1719  1.5 × 24,                                                                       ΔH.sub.r *(298 K.) = -2200 kJ                                            mol.sup.-1,                                     [II-338]                                                                           YCl.sub.3 (cr) + 12F(g) → YF.sub.3 (cr) + 3ClF.sub.3 (g)            -1000      12 × 79                                                                        -1719  3 × -159,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2144 kJ                                       mol.sup.-1,                                     [II-339]                                                                           YH.sub.2 (cr) + 5F(g) → YF.sub.3 (cr) + 2HF(g)                      -226       5 × 29                                                                         -1719  2 × -272,                                                                       ΔH.sub.r.sup.0 (298 K.) = - 2432 kJ                                      mol.sup.-1                                      -185       5 × 62                                                                         -1645  2 × -275,                                                                       ΔG.sub.r.sup.0 (298 K.) = -2320 kJ                                       mol.sup.-1                                      and                                                                            [II-340]                                                                           YH.sub.3 (cr) + 6F(g) → YF.sub.3 (cr) + 3HF(g)                      -268       6 × 79                                                                         -1719  3 × -272,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2741 kJ                                       mol.sup.-1                                      -209       6 × 62                                                                         -1645  3 × -275,                                                                       ΔG.sub.r.sup.0 (298 K.) = -2633 kJ                                       mol.sup.-1.                                     [II-341]                                                                           Y.sub.2 O.sub.3 (cr) + 10H(g) → 2YH.sub.2 (cr) + 3H.sub.2               O(g)                                                                       -1905      10 × 218                                                                       2 × -226                                                                        3 × 242,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1453 kJ                                       mol.sup.-1                                      -1817      10 × 203                                                                       2 × -185                                                                        3 × -229,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1270 kJ                                       mol.sup.-1 ,                                    [II-342]                                                                           Y.sub.2 O.sub.3 (cr) + 12H(g) → 2YH.sub.3 (cr) + 3H.sub.2               O(g)                                                                       -1905      12 × 218                                                                       2 × -268                                                                        3 × -242,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1973 kJ                                       mol.sup.-1                                      -1817      12 × 203                                                                       2 × -209                                                                        3 × -229,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1724 kJ                                       mol.sup.-1,                                     [II-343]                                                                           YCl.sub.3 (cr) + 5H(g) → YH.sub.2 (cr) + 3HCl(g)                    -1000      5 × 218                                                                        -226   3 × -92,                                                                        ΔH.sub.r.sup.0 (298 K.) = -592 kJ                                        mol.sup.-1,                                     [II-344]                                                                           YCl.sub.3 (cr) + 6H(g) → YH.sub.3 (cr) + 3HCl(g)                    -1000      6 × 218                                                                        -268   3 × -92,                                                                        ΔH.sub.r.sup.0 (298 K.) = -852 kJ                                        mol.sup.-1,                                     [II-345]                                                                           YF.sub. 3 (cr) + 5H(g) → YH.sub.2 (cr) + 3HF(g)                     -1719      5 × 218                                                                        -226   3 × -272,                                                                       ΔH.sub.r.sup.0 (298 K.) = -413 kJ                                        mol.sup.-1                                      -1645      5 × 203                                                                        -185   3 × -275,                                                                       ΔG.sub.r.sup.0 (298 K.) = -380 kJ                                        mol.sup.-1                                      and                                                                            [II-346]                                                                           YF.sub.3 (cr) + 6H(g) → YH.sub.3 (cr) + 3HF(g)                      -1719      6 × 218                                                                        -268   3 × -272,                                                                       ΔH.sub.r.sup.0 (298 K.) = -673 kJ                                        mol.sup.-1                                      -1645      6 × 203                                                                        -209   3 × -275,                                                                       ΔG.sub.r.sup.0 (298 K.) = -607 kJ                                        mol.sup.-1.                                     __________________________________________________________________________

Thus, for the volatilization of yttrium species we have the choice of three procedures:

O+F*

H+F

F* (in the absence of YF₃).

J. The Lanthanides

1. THERMODYNAMICS

                  TABLE II-10                                                      ______________________________________                                         LANTHANIDE OXIDES                                                              THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                MO(g)          M.sub.2 O.sub.3 (cr)                                                                        MO.sub.2 (cr)                                      ______________________________________                                         La     -121/-145   -1794/-1706                                                 Ce     -128/-149   -1796/-1706  -1089/-1025                                    Pr     ˜-160/--                                                                             -1810/--     -949/--                                        Nd     ˜-130/--                                                                             -1808/-1721                                                 Pm     NO DATA                                                                 Sm     ˜-130/--                                                                             -1823/-1735                                                 Eu     ˜-130/--                                                                             -1663/--                                                    Gd     ˜-70/--                                                                              -1820/--                                                    Tb     ˜-80/--                                                                              -1865/--     -972/--                                        Dy     ˜-80/--                                                                              -1863/-1772                                                 Ho     ˜-90/--                                                                              -1881/-1791                                                 Er     ˜-50/--                                                                              -1898/-1809                                                 Tm     ˜-80/--                                                                              -1889/-1794                                                 Yb                 -1815/-1727                                                 Lu     -15/-41     -1878/-1789                                                 ______________________________________                                          (all data from Ref. <B>).                                                

                  TABLE II-11                                                      ______________________________________                                         LANTHANIDE CHLORIDES                                                           THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                MCl.sub.2 (Cr)  MCl.sub.3 (cr)                                                                              MCl.sub.3 (g)                                     ______________________________________                                         La                  -1071/-1114a -741/--                                       Ce                  -1054/-978   -728/--                                       Pr                  -1057/--     -782/--                                       Nd      -682/--     -1041/--     -724/--                                       Pm      NO DATA                                                                Sm      -816/--     -1026/--                                                   Eu      -824/--     -936/--                                                    Gd                  -1008/--                                                   Tb                  -997/--                                                    Dy                  -1000/--                                                   Ho                  -1005/--     -703/--                                       Er                  -999/--      -699/--                                       Tm                  -987/--      -695/--                                       Yb      -800/--     -960/--                                                    Lu                  -946/--      -649/--                                       ______________________________________                                          (all data from Ref. <B>, except for a, Ref. <II18>).                     

                                      TABLE II-12                                  __________________________________________________________________________     LANTHANIDE FLUORIDES                                                           THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                MF(g)   MF.sub.2 (g)                                                                        MF.sub.3 (cr)        MF.sub.3 (g)                                 <B>     <B>  (<B>  <II-19>ff                                                                               <II-23>)                                                                             <B>                                          __________________________________________________________________________     La                 -1782a/-1816a                                                                           -1657/--                                           Ce                 -1778b/-1813b                                                                           -1636/--                                           Pr                          -1623/--                                           Nd -159/--                                                                             -690/--                                                                             -1657/--                                                                             -1669c/-1703c                                                                           -1610/--                                                                             -1280/--                                     Pm                          -1602/--                                           Sm -264/--   -1778/--       -1623/--                                                                             -1372/--                                     Eu -293/--                  -1531/--                                           Gd -172/--                                                                             -707/--             -1586/--                                                                             -1297/--                                     Tb                          -1569/--                                           Dy -180/--                  -1561/--                                           Ho -180/--                                                                             -682/--                                                                             -1707/--                                                                             -1707d/-1741d                                                                           - 1548/--                                                                            -1230/--                                     Er -188/--                                                                             -686/--                                                                             -1711/--       -1536/--                                                                             -1230/--                                     Tm                          -1531/--                                           Yb                          -1469/--                                           Lu                          -1536/--                                           __________________________________________________________________________      (a, 5Ref. <II19>; b, Ref. <II20>; c, Ref. <II21>; d, Ref. <II22>).       

                  TABLE II-13                                                      ______________________________________                                         LANTHANIDE DIHYDRIDES (cr)                                                     THERMODYNAMIC DATA                                                             H.sub.f.sup.0 (298 K.)/G.sub.f.sup.0 (298 K.)                                  (kJ mol.sup.-1)                                                                <B>             <II-24>     <II-25>                                            ______________________________________                                         La                  -189/-205   -209/-163                                      Ce      -205/-163   -205/-222   -205/-163                                      Pr      -198/-154   -197/-213   -209/-163                                      Nd      -192/--     -192/-209   -209/-167                                      Pm      NO DATA                                                                Sm                      -201/-159                                              Eu      NO DATA                                                                Gd      -190/--             -197/-159                                          Tb                          -213/-172                                          Dy                          -222/-175                                          Ho      -216/--             -226/-180                                          Er      -205/--             -226/-180                                          Tm                          -226/-180                                          Tb      -176/--             -180/-138                                          Lu                          -209/-163                                          ______________________________________                                    

It is well known that the lanthanides are very similar in their chemistries. The `outer` electronic structures of scandium, yttrium and lanthanum are 3d 4s², 4d 5s² and 5d 6s², respectively. For lanthanum, however, a new factor enters the picture. For lanthanum and the following fourteen elements the 4ƒ levels and the 5d levels are very close in energy. Only four of these fifteen elements (the lanthanides) have a 5d electron in their ground states. These are La, Ce, Gd and Lu. These similarities are reflected in many of the thermodynamic values of these elements.

Referring to TABLE II-10. we find that the enthalpies of formation of the sesquioxides are all relatively close together except for that of Eu. The average value, including Eu, is -1829 kJ mol⁻¹. The average absolute deviation is 43 kJ mol⁻¹ (2.4%) and the root mean square deviation is 58 kJ mol⁻¹ (3.2%). The deviation of the value for Eu from the average value is 166 kJ mol⁻ (9.1%). The deviation of the value for Sc is 80 kJ mol⁻¹ (4.4%). For the purpose of the calculations in the SECTIONS which follow we shall assume the following enthalpies of formation.

sesquioxide as reactant ΔH.sub.ƒ⁰ (O₁.5)=-1898 kJ mol⁻¹ as product, ΔH.sub.ƒ⁰ (O₁.5 ')=-1663 kJ mol⁻¹

dioxide as reactant, ΔH.sub.ƒ⁰ (O₂)=-1089 kJ mol⁻¹ as product, ΔH.sub.ƒ⁰ (O₂ ')=-972 kJ mol⁻¹

The rule which is followed here is to use the value which is largest in magnitude for the reactant and the value which is smallest in magnitude for the product. (`Magnitude` here means, of course, `absolute magnitude`. This terminology precaution is necessary since all of the values are negative.) By using these extremum values we can use a single calculation (`worst case` analysis) to cover all fifteen elements.

Referring now to TABLE II-11. we find that a similar situation exists relative to the enthalpies of formation of the trichlorides. The average value is -1006 kJ mol⁻¹ with an average absolute deviation of 31 kJ mol⁻¹ (3.1%) and a root mean square deviation of 35 kJ mol-1 (3.5%). The deviation of the value for Sc is 81 kJ mol⁻¹ (8.1%). We shall assume in the calculations which follow the following enthalpies of formation;

dichloride as reactant, ΔH.sub.ƒ⁰ (Cl₂)=-824 kJ mol⁻¹ as product, ΔH.sub.ƒ⁰ (Cl₂)=-682 kJ mol⁻¹

trichloride as reactant, ΔH.sub.ƒ⁰ (Cl₃)=-1071 kJ mol⁻¹ as product, ΔH.sub.ƒ⁰ (Cl₃)=-936 kJ mol⁻¹.

For the trifluorides we require the enthalpies of formation for both the crystalline and gaseous states. As is indicated in TABLE II-12, we have only limited data for the gaseous species. Although we have extensive data on the crystalline states from <II-23>, the values are consistently lower than those from the more recent references, <B>, <II-19>, <II-20>, <II-21> and <II-22>. From <II-23> the average value of the enthalpy of formation of the crystalline trifluorides is -1575 kJ mol⁻¹ with an average absolute deviation of 42 kJ mol⁻¹ (2.7%) and a root mean square deviation of 49 kJ mol⁻¹ (3.1%). From the newer references the average value is -1736 kJ mol⁻¹ with an average absolute deviation of 43 kJ mol⁻¹ (2.5%) and a root mean square deviation of 46 kJ mol⁻¹ (2.6%). The deviation of the value for Sc is 107 kJ mol⁻¹ (6.2%).

The average value of the enthalpy of formation of the gaseous trifluorides is -1282 kJ mol⁻¹ with an absolute deviation of 42 kJ mol⁻¹ (3.3%) and a root mean square deviation of 52 kJ mol⁻¹ (4.1%). The deviation of the value for scandium is 35 kJ mol⁻¹ (2.7%). For those elements for which we can calculate the enthalpies of sublimation the largest value is for Er, 481 kJ mol⁻¹. For this value the `times four` criterion is 1924 kJ mol⁻¹. In the calculations which follow wse shall use the following extremum values:

monofluoride as product, ΔH.sub.ƒ⁰ (F)=-159 kJ mol⁻¹

difluoride as product, ΔH.sub.ƒ⁰ (F₂)=-682 kJ mol⁻¹

trifluoride as reactant, ΔH.sub.ƒ⁰ (F₃)=-1782 kJ mol⁻¹ as product, ΔH.sub.ƒ⁰ (F₃)=-1469 kJ mol⁻¹

`times four` criterion, 1924 kJ mol⁻¹

For the dihydrides the average value of the enthalpies of formation from <II-25> (the most recent reference as well as the most complete) is -210 kJ mol⁻¹ with an average absolute deviation of 9 kJ mol⁻¹ (4.3%) and a root mean square deviation of 13 kJ mol⁻¹ (6.2%). The extremum values which will be used are

dihydride as reactant ΔH.sub.ƒ⁰ (H₂)=-226 kJ mol⁻¹

as product, ΔH.sub.ƒ⁰ (H₂)=-180 kJ mol⁻¹.

For the enthalpies of formation of the nitrates we have data for only five elements:

La -1254 kJ mol⁻¹

Ce -1226

Pr -1229

Nd -1231

Sm -1212.

The average value is -1230 kJ mol⁻¹ with an average absolute deviation of 10 kJ mol⁻¹ (0.81%) and a root mean square deviation of 14 kJ mol⁻¹ (1.1%). The spread of these data is quite small. These elements, however, are those with the lowest number of 4ƒ electrons. We shall find that, even when large deviations from this average value are assumed, the reactions involving the nitrates are quite exothermic.

2. MONOXYGEN CHEMISTRIES

    __________________________________________________________________________     [II-347]                                                                           M(cr) + O(g) → MO(g)                                                0       249   -15,        ΔH.sub.r.sup.0 (298 K.) = -264 kJ                                        mol.sup.-1,                                          [II-348]                                                                           M(cr) + 1.5O(g) → 0.5M.sub.2 O.sub.3 (cr)                           0       1.5 × 249                                                                      0.5 × -1663,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1205 kJ                                       mol.sup.-1,                                          [II-349]                                                                           M(cr) + 2O(g) → MO.sub.2 (cr)                                       0       2 × 249                                                                        -972,       ΔH.sub.r.sup.0 (298 K.) = -1470 kJ                                       mol.sup.-1,                                          [II-350]                                                                           MCl.sub.2 (cr) + 5.5O(g) → 0.5M.sub.2 O.sub.3 (cr)                      + 2ClO.sub.2 (g)                                                           -824    5.5 × 249                                                                      0.5 × -1663                                                                     2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1173 kJ                                       mol.sup.-1,                                          [II-351]                                                                           MCl.sub.2 (cr) + 6O(g) → MO.sub.2 (cr) + 2ClO.sub. 2 (g)            -824    6 × 249                                                                        -972   2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1438 kJ                                       mol.sup.-1,                                          [II-352]                                                                           MCl.sub.3 (cr) + 7.5O(g) → 0.5M.sub.2 O.sub.3 (cr)                      + 3ClO.sub.2 (g)                                                           -1071   7.5 × 249                                                                      0.5 × -1663                                                                     3 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1322 kJ                                       mol.sup.-1,                                          [II-353]                                                                           MCl.sub.3 (cr) + 8O(g) → MO.sub.2 (cr) + 3ClO.sub.2 (g)             -1071   8 × 249                                                                        -972   3 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1587 kJ                                       mol.sup.-1,                                          [II-354]                                                                           MF.sub.3 (cr) + 7.5O(g) → 0.5M.sub.2 O.sub.3 (cr) + 3FO.sub.2           (g)                                                                        -1782   7.5 × 249                                                                      0.5 × -1663                                                                     3 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -878 kJ                                        mol.sup. -1,                                         [II-355]                                                                           MF.sub.3 (cr) + 8O(g) → MO.sub.2 (cr) + 3FO.sub.2 (g)               -1782   8 × 249                                                                        -972   3 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1143 kJ                                       mol.sup.-1,                                          [II-356]                                                                           MH.sub.2 (cr) + 2.5O(g) → 0.5M.sub.2 O.sub.3 (cr) + H.sub.2             O(g)                                                                       -226    2.5 × 249                                                                      0.5 × -1663                                                                     -242,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1470 kJ                                       mol.sup.-1                                           and                                                                            [II-357]                                                                           MH.sub.2 (cr) + 3O(g) → MO.sub.2 (cr) + H.sub.2 O(g)                -226    3 × 249                                                                        -972   -242,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1735 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

3. MONOXYGEN PLUS NITROGEN DIOXIDE CHEMISTRIES

    __________________________________________________________________________     [II-358]                                                                           M(cr) + 3O(g) + 3NO.sub.2 (g) → M(NO.sub.3).sub.3 (cr)              0       3 × 249                                                                       3 × 33                                                                       -1230,   ΔH.sub.r.sup.0 (298 K.) = -2076 kJ                                       mol.sup.-1,                                          [II-359]                                                                           M.sub.2 O.sub.3 (cr) + 3O(g) + 6NO.sub.2 (g) → M(NO.sub.3).sub.         3 (cr)                                                                     -1898   3 × 249                                                                       6 × 33                                                                       2 × -1230,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1507 kJ                                       mol.sup.-1,                                          [II-360]                                                                           MO.sub.2 (cr) + O(g) + 3NO.sub.2 (g) → M(NO.sub.3).sub.3 (cr)       -1089   249  3 × 33                                                                       -1230,   ΔH.sub.r.sup.0 (298 K.) = -489 kJ                                        mol.sup.-1,                                          [II-361]                                                                           MCl.sub.2 (cr) + 7O(g) + 3NO.sub.2 (g) → M(NO.sub.3).sub.3              (cr) + 2ClO.sub.2 (g)                                                      -824    7 × 249                                                                       3 × 33                                                                       -1230                                                                              2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2044 kJ                                       mol.sup.-1,                                          [II-362]                                                                           MCl.sub.3 (cr) + 9O(g) + 3NO.sub.2 (g) → M(NO.sub.3).sub.3              (cr) + 3ClO.sub.2 (g)                                                      -1071   9 × 249                                                                       3 × 33                                                                       -1230                                                                              3 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2193 kJ                                       mol.sup.-1,                                          [II-363]                                                                           MF.sub.3 (cr) + 9O(g) + 3NO.sub.2 (g) → M(NO.sub.3).sub.3 (cr)          + 3FO.sub.2 (g)                                                            -1782   9 × 249                                                                       3 × 33                                                                       -1230                                                                              3 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1749 kJ                                       mol.sup.-1                                           and                                                                            [II-364]                                                                           MH.sub.2 (cr) + 4O(g) + 3NO.sub.2 (g) → M(NO.sub.3).sub.3 (cr)          + H.sub.2 O(g)                                                             -226    4 × 249                                                                        3 × 33                                                                      -1230                                                                              -242,                                                                               ΔH.sub.r.sup.0 (298 K.) = -2341 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

For reactions [II-358], [II-361], [II-362], [II-363] and [II-364] the enthalpy of formation of the nitrate could be zero, and the reactions would still be exothermic. For reaction [II-359] the enthalpy of formation of the nitrate could be -500 kJ mol⁻¹, and the reaction would still be exothermic. For the worst case, reaction [II-360] the enthalpy of formation of the nitrate could be -800 kJ mol⁻¹, and the reaction would still be exothermic. Since all of these deviations from -1230 kJ mol⁻¹ are so large as to be most unlikely, we can reasonably assume that all of the O/NO₂ reactions will go as written.

4. MONOFLUORINE CHEMISTRIES

    __________________________________________________________________________     [II-365]                                                                           M(cr) + F(g) → MF(g)                                                0          79   -159,          ΔH.sub.r.sup.0 (298 K.) = -238 kJ                                        mol.sup.-1,                                     [II-366]                                                                           M(cr) + 2F(g) → MF.sub.2 (g)                                        0          2 × 79                                                                        -682,          ΔH.sub.r.sup.0 (298 K.) = -840 kJ                                        mol.sup.-1,                                     [II-367]                                                                           M(cr) + 3F(g) → MF.sub.3 (g)                                        0          3 × 79                                                                        -1469,         ΔH.sub.r.sup.0 (298 K.) = -1706 kJ                                       mol.sup.-1,                                     [II-368]                                                                           M(cr) + 3F*(g) → MF.sub.3 (g)                                       0          3 × 245                                                                       -1469,         ΔH.sub.r *(298 K.) = -2204 kJ                                            mol.sup.-1,                                     [II-369]                                                                           0.5M.sub.2 O.sub.3 (cr) + 6F(g) → MF.sub.3 (cr) + 1.5OF.sub.2           (g)                                                                        0.5 × -1898                                                                         6 × 79                                                                        -1469                                                                              1.5 × 24,                                                                            ΔH.sub.r.sup.0 (298 K.) = -958 kJ                                       mol.sup.-1,                                     [II-370]                                                                           0.5M.sub.2 O.sub.3 (cr) + 6F*(g) → MF.sub.3 (cr) + 1.5OF.sub.2          (g)                                                                        0.5 × -1898                                                                         6 × 245                                                                       -1469                                                                              1.5 × 24,                                                                           ΔH.sub.r *(298 K.) = -1954 kJ                                            mol.sup.-1,                                     [II-371]                                                                           MO.sub.2 (cr) + 7F(g) → MF.sub.3 (cr) + 2OF.sub.2 (g)               -1089      7 × 79                                                                        -1469                                                                              2 × 24,                                                                             ΔH.sub.r.sup.0 (298 K.) = -885 kJ                                        mol.sup.-1,                                     [II-372]                                                                           MO.sub.2 (cr) + 7F*(g) → MF.sub.3 (cr) + 2OF.sub.2 (g)              -1089      7 × 245                                                                       -1469                                                                              2 × 24,                                                                             ΔH.sub.r *(298 K.) = -2047 kJ                                            mol.sup.-1,                                     [II-373]                                                                           M(NO.sub.3).sub.3 (cr) + 30F(g) → MF.sub.3 (cr) + 3NF.sub.3             (g) + 9OF.sub.2 (g)                                                        -1230      30 × 79                                                                       -1469                                                                              3 × -124                                                                       9 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2765 kJ                                       mol.sup.-1,                                     [II-374]                                                                           M(NO.sub.3).sub.3 (cr) + 30F*(g) → MF.sub.3 (cr) + 3NF.sub.3            (g) + 9OF.sub.2 (g)                                                        -1230      30 × 245                                                                      -1469                                                                              3 × -124                                                                       9 × 24,                                                                       ΔH.sub.r *(298 K.) = -7745 kJ                                            mol.sup.-1,                                     [II-375]                                                                           MCl.sub.2 (cr) + 9F(g) → MF.sub.3 (cr) + 2ClF.sub.3 (g)             -824       9 × 79                                                                        -1464                                                                              2 × -159,                                                                           ΔH.sub.r.sup.0 (298 K.) = -1669 kJ                                       mol.sup.-1,                                     [II-376]                                                                           MCl.sub.2 (cr) + 9F*(g) → MF.sub.3 (cr) + 2ClF.sub.3 (g)            -824       9 × 245                                                                       -1464                                                                              2 × -159,                                                                           ΔH.sub.r *(298 K.) = -3163 kJ                                            mol.sup.-1,                                     [II-377]                                                                           MCl.sub.3 (cr) + 12F(g) → MF.sub.3 (cr) + 3ClF.sub.3 (g)            -1071      12 × 79                                                                       -1464                                                                              3 × -159,                                                                           ΔH.sub.r.sup.0 (298 K.) = -1818 kJ                                       mol.sup.-1,                                     [II-378]                                                                           MCl.sub.3 (cr) + 12F*(g) → MF.sub.3 (cr) + 3ClF.sub.3 (g)           -1071      12 × 245                                                                      -1469                                                                              3 × -159,                                                                           ΔH.sub.r *(298 K.) = -3810 kJ                                            mol.sup.-1                                      and                                                                            [II-379]                                                                           MH.sub.2 (cr) + 5F(g) → MF.sub.3 (cr) + 2HF(g)                      -226       5 × 79                                                                        -1464                                                                              2 × -272,                                                                           ΔH.sub.r.sup.0 (298 K.) = -2177 kJ                                       mol.sup.-1.                                     __________________________________________________________________________

Thus, we find that even under the extremum conditions monofluorine in its excited state will volatilize all of the lanthanide species analyzed here. Furthermore, even ground state monofluorine will volatilize the dihydrides and the nitrates will volatilize the dihydrides and the nitrates (unless the enthalpy of formation is more negative than -2000 kJ mol⁻¹ which is most unlikely.)

5. MONOHYDROGEN CHEMISTRIES

    __________________________________________________________________________     [II-380]                                                                           M(cr) + 2H(g) → MH.sub.2 (cr)                                       0       2 × 218                                                                       -180,            ΔH.sub.r.sup.0 (298 K.) = -616 kJ                                        mol.sup.-1,                                      [II-381]                                                                           M.sub.2 O.sub.3 (cr) + 10H(g) → 2MH.sub.2 (cr) + 3H.sub.2               O(g)                                                                       -1898   10 × 218                                                                      2 × -180                                                                       3 × -242,                                                                           ΔH.sub.r.sup.0 (298 K.) = -1368 kJ                                       mol.sup.-1,                                      [II-382]                                                                           MO.sub.2 (cr) + 6H(g) → MH.sub.2 (cr) + 2H.sub.2 O(g)               -1089   6 × 218                                                                       -180  2 × -242,                                                                           ΔH.sub.r.sup.0 (298 K.) = -883 kJ                                        mol.sup.-1,                                      [II-383]                                                                           M(NO.sub.3).sub.3 (cr) + 29H(g) → MH.sub.2 (cr) + 3NH.sub.3             (g) + 9H.sub.2 O(g)                                                        -1230   29 × 218                                                                      -180  3 × - 46, 9 × -242,                                                           ΔH.sub.r.sup.0 (298 K.) = -7588 kJ                                       mol.sup.-1,                                      [II-384]                                                                           MCl.sub.2 (cr) + 4H(g) → MH.sub.2 (cr) + 2HCl(g)                    -824    4 × 218                                                                       -180  2 × -92,                                                                            ΔH.sub.r.sup.0 (298 K.) = -412 kJ                                        mol.sup.-1,                                      [II-385]                                                                           MCl.sub.3 (cr) + 5H(g) → MH.sub.2 (cr) + 3HCl(g)                    -1071   5 × 218                                                                       -180  3 × -92,                                                                            ΔH.sub.r.sup.0 (298 K.) = -475 kJ                                        mol.sup.-1                                       and                                                                            [II-386]                                                                           MF.sub.3 (cr) + 5H(g) → MH.sub.2 (cr) + 3HF(g)                      -1782   5 × 218                                                                       -180  3 × -272,                                                                           ΔH.sub.r.sup.0 (298 K.) = -304 kJ                                        mol.sup.-1.                                      __________________________________________________________________________

6. SUMMARY OF GROUP IIIB. AND LANTHANIDE PROCEDURES

Thus, we find that for the volatilization of the GROUP III B and lanthanide species we have the choice of four procedures.

O+F*

O/NO₂ +F

H+F

F* (in the absence of MF₃).

(In addition it should be noted that the chemistries discussed here can be used to synthesize anhydrous lanthanide compounds. For example, reactions [II-358] and/or [II-359] can be used to synthesize anhydrous nitrates.)

K. Group IV B.

1. THERMODYNAMICS

Of the various chlorides only titanium tetrachloride will vaporize spontaneously in the Apparatus. Zirconium tetrachloride, however, is marginal by the criterion of [II-2]. The enthalpies of sublimation of the tetrafluorides of titanium, zirconium and hafnium are, 98, 237 and 260 kJ mol⁻¹, respectively. Thus, the `times four` criteria are 392, 948 and 1040 kJ mol⁻¹ , respectively.

                  TABLE II-14                                                      ______________________________________                                         GROUP IVB                                                                      THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES Ti          Zr          Hf                                             ______________________________________                                         MO(cr)  -543/-513                                                              (l)     -494/-472                                                              (g)     +54/+25     +59/+33     +50a/--                                        M.sub.2 O.sub.3 (cr)                                                                   -1521/-1434                                                            (l)     -1418/-1346                                                            MO.sub.2 (cr)                                                                          -945/-889   -1097/-1040 -1145a/-1088a                                  (l)     -894/-845   -1023/-973                                                 (g)     -305/-313   -286/-295                                                  MO.sub.3 (cr)       -1008a/--                                                  MCl(g)  +154/+123   +205/+174                                                  MCl.sub.2 (cr)                                                                         -515/-466   -431/-386                                                  (l)                 -412/-370                                                  (g)     -237/-245   -186/-195                                                  MCl.sub.3 (cr)                                                                         -722/-654   -714/-646                                                  (g)     -539/-525   -524/-514                                                  MCl.sub.4 (cr)                                                                         -815/-735   -981/-890   -990a/-901a                                    (l)     -804/-728                                                              (g)     -763/-727   - 870/-835  -884a/--                                       MF(g)   -67/-98     +83/+52                                                    MF.sub.2 (cr)       -962/-913                                                  (l)                 -937/-895                                                  (g)     -688/-695   -558/-571                                                  MF.sub.3 (cr)                                                                          -1432/-1313 -1402/-1326                                                (g)     -1189/-1176 -1105/-1094                                                MF.sub.4 (cr)                                                                          -1649/-1559 -1911/-1810 1930a/1830a                                    (g)     -1551/-1515 -1674/-1636 -1670a/--                                      MH.sub.2 (cr)                                                                          -120a/-80a  -169a/-129a                                                ______________________________________                                          (a, Ref. <B>)                                                            

2. TITANIUM

    __________________________________________________________________________     [II-387]                                                                           Ti(cr) + O(g) → TiO(cr)                                             0          249   -543,  ΔH.sub.r.sup.0 (298 K.) = -792 kJ                                        mol.sup.-1                                             0          232   -513,  ΔG.sub.r.sup.0 (298 K.) = -745 kJ                                        mol.sup.-1,                                            [II-388]                                                                           TiO(cr) + 0.5O(g) → 0.5Ti.sub.2 O.sub.3 (cr)                        -543       0.5 × 249                                                                      0.5 × -1521,                                                                    ΔH.sub.r.sup.0 (298 K.) = -342 kJ                                        mol.sup.-1                                             -513       0.5 × 232                                                                      0.5 × -1434,                                                                    ΔG.sub.r.sup.0 (298 K.) = -320 kJ                                        mol.sup.-1                                             and                                                                            [II-389]                                                                           0.5Ti.sub.2 O.sub.3 (cr) + 0.5O(g) → TiO.sub.2 (cr)                 0.5 × -1521                                                                         0.5 × 249                                                                      -945,  ΔH.sub.r.sup.0 (298 K.) = -309 kJ                                        mol.sup.-1                                             0.5 × -1434                                                                         0.5 × 232                                                                      -894,  ΔG.sub.r.sup.0 (298 K.) = -293 kJ                                        mol.sup.-1 .                                           __________________________________________________________________________

The enthalpy of melting of titanium monoxide is 49 kJ mol⁻¹. Thus, by the `times four` criterion [II-387] will yield the liquid monoxide. By [II-388[ the reaction will continue with the formation of the sesquioxide. The enthalpy of melting of the sesquioxide is 103 kJ mol⁻¹. Thus, by the `times four` criterion (412<792+342) the liquid sesquioxide will be formed. By [II-389] the reaction will continue to the dioxide. The enthalpy of melting of the dioxide is 51 kJ mol⁻¹.

If the sesquioxide is formed from the crystalline monoxide, the liquid sesquioxide will not form. If, however, sufficient monoxygen is present to take the reaction to the dioxide, the liquid dioxide will form, and all of the monoxide and sesquioxide will be converted to the dioxide. Thus, in the subsequent reactions we need consider only the dioxide as the product of monoxygen reactions.

    __________________________________________________________________________     [II-390]                                                                           TiCl.sub.2 (cr) + 6O(g) → TiO.sub.2 (cr) + 2ClO.sub.2 (g)           -515    6 × 249                                                                       -945                                                                               2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1720 kJ                                       mol.sup.-1                                               -466    6 × 232                                                                       -889                                                                               2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1575 kJ                                       mol.sup.-1,                                              [II-391]                                                                           TiCl.sub.3 (cr) + 8O(g) → TiO.sub.2 (cr) + 3ClO.sub.2 (g)           -722    8 × 249                                                                       -945                                                                               3 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1909 kJ                                       mol.sup.-1                                               -654    8 × 232                                                                       -889                                                                               3 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1731 kJ                                       mol.sup.-1,                                              [II-392]                                                                           TiF.sub.3 (cr) + 8O(g) → TiO.sub.2 (cr) + 3FO.sub.2 (g)             -1432   8 × 249                                                                       -945                                                                               3 ×  13,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1466 kJ                                       mol.sup.-1                                               -1313   8 × 232                                                                       -889                                                                               3 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1351 kJ                                       mol.sup.-1,                                              [II-392]                                                                           TiF.sub.4 (cr) + 10O(g) → TiO.sub.2 (cr) + 4FO.sub.2 (g)            -1649   10 × 249                                                                      -945                                                                               4 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1734 kJ                                       mol.sup.-1                                               -1559   10 × 232                                                                      -889                                                                               4 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1542 kJ                                       mol.sup.-1                                               and                                                                            [II-394]                                                                           TiH.sub.2 (cr) + 3O(g) → TiO.sub.2 (cr) + H.sub.2 O(g)              -120    3 × 249                                                                       -945                                                                               -242,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1814 kJ                                       mol.sup.-1                                               -80     3 × 232                                                                       -889                                                                               -229,                                                                               ΔG.sub.r.sup.0 (298 K.) = -1734 kJ                                       mol.sup.-1,                                              [ II-395]                                                                          Ti(cr) + F(g) → TiF(g)                                              0       79   -67,     ΔH.sub.r.sup.0 (298 K.) = -146 kJ mol.sup.-1       0       62   -98,     ΔG.sub.r.sup.0 (298 K.) = -160 kJ                                        mol.sup.-1,                                              [II-396]                                                                           Ti(cr) + 2F(g) → TiF.sub.2 (g)                                      0       2 × 79                                                                        -688,    ΔH.sub.r.sup.0 (298 K.) = -846 kJ mol.sup.-1       0       2 × 62                                                                        -695,    ΔG.sub.r.sup.0 (298 K.) = -819 kJ                                        mol.sup.-1,                                              [II-397]                                                                           Ti(cr) + 3F(g) → TiF.sub.3 (cr)                                     0       3 × 79                                                                        -1432,   ΔH.sub.r.sup.0 (298 K.) = -1667 kJ                                       mol.sup.-1                                               0       3 × 62                                                                        -1313,   ΔG.sub.r.sup.0 (298 K.) = -1499 kJ                                       mol.sup.-1                                               and                                                                            [II-398]                                                                           Ti(cr) + 4F(g) → TiF.sub.4 (cr)                                     0       4 × 79                                                                        -1649,   Δ H.sub.r.sup.0 (298 K.) = -1965 kJ                                      mol.sup.-1                                               0       4 × 62                                                                        -1559,   ΔG.sub.r.sup.0 (298 K.) = -1807 kJ                 __________________________________________________________________________                           mol.sup.-1.                                         

The enthalpy of sublimation of titanium trifluoride is 243 kJ mol⁻¹, and the `times four` criterion is 972 kJ mol-1. Thus, the trifluoride formed by [II-397] as well as the tetrafluoride formed by [II-398] will volatilize. Thus, we must consider both the trifluoride as well as the tetrafluoride as possible volatilization products.

    __________________________________________________________________________     [II-399]                                                                           0.5Ti.sub.2 O.sub.3 + 6F(g) → TiF.sub.3 (cr) + 1.5OF.sub.2              (g)                                                                        0.5 × -1521                                                                         6 × 79                                                                        -1432                                                                              1.5 × 24,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1110 kJ                                       mol.sup.-1                                           0.5 × -1434                                                                         6 × 62                                                                        -1313                                                                              1.5 × 42,                                                                      ΔG.sub.r.sup.0 (298 K.) = -905 kJ                                        mol.sup.-1,                                          [II-400]                                                                           TiO.sub.2 (cr) + 7F(g) → TiF.sub.3 (cr) + 2OF.sub.2 (g)             -945       7 × 79                                                                        -1432                                                                              2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -992 kJ                                        mol.sup.-1                                           -889       7 × 62                                                                        -1313                                                                              2 × 42,                                                                        ΔG.sub.r.sup.0 (298 K.) = -774 kJ                                        mol.sup.-1,                                          [II-401]                                                                           TiCl.sub.2 (cr) + 9F(g) → TiF.sub.3 (cr) + 2ClF.sub.3 (g)           -515       9 × 79                                                                        - 1432                                                                             2 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1946 kJ                                       mol.sup.-1                                           -466       9 × 62                                                                        -1313                                                                              2 × -119,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1643 kJ                                       mol.sup.-1,                                          [II-402]                                                                           TiCl.sub.3 (cr) + 12F(g) → TiF.sub.3 (cr) + 3ClF.sub.3 (g)          -722       12 × 79                                                                       -1432                                                                              3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2135 kJ                                       mol.sup.-1                                           -654       12 × 62                                                                       -1313                                                                              3 × -119,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1760 kJ                                       mol.sup.-1                                           and                                                                            [II-403]                                                                           TiH.sub.2 (cr) + 5F(g) → TiF.sub.3 (cr) + 2HF(g)                    -120       5 × 79                                                                        -1432                                                                              2 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2251 kJ                                       mol.sup.-1                                           -80        5 × 62                                                                        -1313                                                                              2 × -275,                                                                      ΔG.sub.r.sup.0 (298 K.) = -2093 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

Thus, even without considering the tetrafluoride as the produce or excited state monofluorine as the reactant monofluorine is an effective volatilizing reagent for titanium species.

    __________________________________________________________________________     [II-404]                                                                           Ti(cr) + 2H(g) → TiH.sub.2 (cr)                                     0       2 × 218                                                                       -120,     ΔH.sub.r.sup.0 (298 K.) = -556 kJ                                        mol.sup.-1                                              0       2 × 203                                                                       -80,      ΔG.sub.r.sup.0 (298 K.) = -486 kJ                                        mol.sup.-1,                                             [II-405]                                                                           Ti.sub.2 O.sub.3 (cr) + 10H(g) → 2TiH.sub.2 (cr) + 3H.sub.2             O(g)                                                                       -1521   10 × 218                                                                      -120                                                                               3 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1505 kJ                                       mol.sup.-1                                              -1434   10 × 203                                                                      -80 3 × -229,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1363 kJ                                       mol.sup.-1,                                             [II-406]                                                                           TiO.sub.2 (cr) + 6H(g) → TiH.sub.2 (cr) + 2H.sub.2 O(g)             -945    6 × 218                                                                       -120                                                                               2 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -967 kJ                                        mol.sup.-1                                              -889    6 × 203                                                                       -80 2 × -229,                                                                      ΔG.sub.r.sup.0 (298 K.) = -867 kJ                                        mol.sup.-1,                                             [II-407]                                                                           TiCl.sub.2 (cr) + 4H(g) → TiH.sub.2 (cr) + 2HCl(g)                  -515    4 × 218                                                                       -120                                                                               2 × -92,                                                                       ΔH.sub.r.sup.0 (298 K.) = -661 kJ                                        mol.sup.-1                                              -466    4 × 203                                                                       -80 2 × -95,                                                                       ΔG.sub.r.sup.0 (298 K.) = -616 kJ                                        mol.sup.-1,                                             [II-408]                                                                           TiCl.sub.3 (cr) + 5H(g) → TiH.sub.2 (cr) + 3HCl(g)                  -722    5 × 218                                                                       -120                                                                               3 × -92,                                                                       ΔH.sub.r.sup.0 (298 K.) = -764 kJ                                        mol.sup.-1                                              -654    5 × 203                                                                       -80 3 × -95,                                                                       ΔG.sub.r.sup.0 (298 K.) = -726 kJ                                        mol.sup.-1,                                             [II-409]                                                                           TiF.sub.3 (cr) + 5H(g) → TiH.sub. 2 (cr) + 3HF(g)                   -1432   5 × 218                                                                       -120                                                                               3 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -594 kJ                                        mol.sup.-1                                              -1313   5 × 203                                                                       -80 3 × -275,                                                                      ΔG.sub.r.sup.0 (298 K.) = -607 kJ                                        mol.sup.-1                                              and                                                                            [II-410]                                                                           TiF.sub.4 (cr) + 6H(g) → TiH.sub.2 (cr) + 4HF(g)                    -1649   6 × 218                                                                       -120                                                                               4 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -867 kJ                                        mol.sup.-1                                              -1559   6 × 203                                                                       -80 4 × -275,                                                                      ΔG.sub.r.sup.0 (298 K.) = -839 kJ                 __________________________________________________________________________                            mol.sup.-1.                                        

Thus, we have a choice of three procedures for the volatilization of titanium species:

O+F

H+F

F (in the absence of TiF₄).

3. ZIRCONIUM

For the three crystalline fluorides of zirconium listed in TABLE II-14. the enthalpies of sublimation are 404 kJ mol⁻¹, 297 kJ mol⁻¹ and 237 kJ mol⁻¹ for the difluoride, the trifluoride and the tetrafluoride, respectively. The `times four` criteria, therefore, are 1616 kJ mol⁻¹, 1188 kJ mol⁻¹ and 948 kJ mol⁻¹.

    __________________________________________________________________________     [II-411]                                                                           Zr(cr) + O(g) → ZrO(g)                                              0        249   59,  ΔH.sub.r.sup.0 (298 K.) = -190 kJ mol.sup.-1         0        232   33,  ΔG.sub.r.sup.0 (298 K.) = -199 kJ mol.sup.-1,        [II-412]                                                                           Zr(cr) + 2O(g) → ZrO.sub.2 (cr)                                     0        2 × 249                                                                        -1097,                                                                              ΔH.sub.r.sup.0 (298 K.) = -1595 kJ mol.sup.-1        0        2 × 232                                                                        -1040,                                                                              ΔG.sub.r.sup.0 (298 K.) = -1504 kJ mol.sup.-1        and                                                                            [II-413]                                                                           ZrO.sub.2 (cr) + O(g) → ZrO.sub.3 (cr)                              -1097    249   -1008,                                                                              ΔG.sub.r.sup.0 (298 K.) = -160 kJ                    __________________________________________________________________________                         mol.sup.-1.                                           

The enthalpy of melting of zirconium dioxide is 74 kJ mol⁻¹, and the `times four` criterion is 296 kJ mol⁻¹. Thus, reaction [II-412] will produce liquid zirconium dioxide. By [II-413] the reaction will continue to the trioxide. Since the ΔH_(r) ⁰ for [II-413] is rather small, and since very little is known about the trioxide, we shall assume that the end product of the monoxygen reactions is the dioxide.

    __________________________________________________________________________     [II-414]                                                                           ZrCl.sub.2 (cr) + 6O(g) → ZrO.sub.2 (cr) + 2ClO.sub.2 (g)           -431    6 × 249                                                                       -1097                                                                              2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1956 kJ                                       mol.sup.-1                                               -386    6 × 232                                                                       -1040                                                                              2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1866 kJ                                       mol.sup.-1,                                              [II-415]                                                                           ZrCl.sub.3 (cr) + 8O(g) → ZrO.sub.2 (cr) + 3ClO.sub.2 (g)           -714    8 × 249                                                                       -1097                                                                              3 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2069 kJ                                       mol.sup.-1                                               -646    8 × 232                                                                       -1040                                                                              3 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1890 kJ                                       mol.sup.-1,                                              [II-416]                                                                           ZrCl.sub.4 (cr) + 10O(g) → ZrO.sub.2 (cr) + 4ClO.sub.2 (g)          -981    10 × 247                                                                      -1097                                                                              4 × 102,                                                                      Δ H.sub.r.sup.0 (298 K.) = -2198 kJ                                      mol.sup.-1                                               -890    10 × 232                                                                      -1040                                                                              4 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1990 kJ                                       mol.sup.-1,                                              [II-418]                                                                           ZrF.sub.2 (cr) + 6O(g) → ZrO.sub.2 (cr) + 2FO.sub.2 (g)             -962    6 × 249                                                                       -1097                                                                              2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1603 kJ                                       mol.sup.-1                                               -913    6 × 232                                                                       -1040                                                                              2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1465 kJ                                       mol.sup.-1,                                              [II-419]                                                                           ZrF.sub.3 (cr) + 8O(g) → ZrO.sub.2 (cr) + 3FO.sub.2 (g)             -1402   8 × 249                                                                       -1097                                                                              3 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1648 kJ                                       mol.sup.-1                                               -1326   8 × 232                                                                       -1040                                                                              3 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1489 kJ                                       mol.sup.-1,                                              [ II-420]                                                                          ZrF.sub.4 (cr) + 10O(g) → ZrO.sub.2 (cr) + 4FO.sub.2 (g)            -1911   10 × 249                                                                      -1097                                                                              4 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1624 kJ                                       mol.sup.-1                                               -1810   10 × 232                                                                      -1040                                                                              4 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1442 kJ                                       mol.sup.-1                                               and                                                                            [II-421]                                                                           ZrH.sub.2 (cr) + 3O(g) → ZrO.sub.2 (cr) + H.sub.2 O(g)              -169    3 × 249                                                                       -1097                                                                              -242,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1917 kJ                                       mol.sup.-1                                               -129    3 × 232                                                                       -1040                                                                              -229,                                                                               ΔG.sub.r.sup.0 (298 K.) = -1836 kJ                                       mol.sup.-1.                                              [II-422]                                                                           Zr(cr) + F(g) → ZrF(g)                                              0       79   83,      ΔH.sub.r.sup.0 (298 K.) = +4 kJ mol.sup.-1         0       62   52,      ΔG.sub.r.sup.0 (298 K.) = -10 kJ mol.sup.                                -1,                                                      [II-423]                                                                           Zr(cr) + 2F(g) → ZrF.sub.2 (cr)                                     0       2 × 79                                                                        -962,    ΔH.sub.r.sup.0 (298 K.) = -1120 kJ                                       mol.sup.-1,                                              0       2 × 62                                                                        -913,    ΔG.sub.r.sup.0 (298 K.) = -1037 kJ                                       mol.sup.-1,                                              [II-424]                                                                           Zr(cr) + 3F(g) → ZrF.sub.3 (cr)                                     0       3 × 79                                                                        -1402,   ΔH.sub.r.sup.0 (298 K.) = -1639 kJ                                       mol.sup.-1                                               0       3 × 62                                                                        -1326,   ΔG.sub.r.sup.0 (298 K.) = -1512 kJ                                       mol.sup.-1                                               and                                                                            [II-425]                                                                           Zr(cr) + 4F(g) → ZrF.sub.4 (cr)                                     0       4 × 79                                                                        -1911,   ΔH.sub.r.sup.0 (298 K.) = -2227 kJ                                       mol.sup.-1                                               0       4 × 62                                                                        -1810,   ΔG.sub.r.sup.0 (298 K.) = -2058 kJ                 __________________________________________________________________________                           mol.sup.-1.                                         

Since both [II-424] and [II-424] meet their respective `times four` criteria, we shall consider both the trifluoride and the tetrafluoride as potential volatilized products.

    __________________________________________________________________________     [II-426]                                                                           ZrO.sub.2 (cr) + 7F(g) → ZrF.sub.3 (cr) + 2OF.sub.2 (g)             -1097   7 × 79                                                                        -1402                                                                              2 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -810 kJ mol.sup.-1       -1040   7 × 62                                                                        -1326                                                                              2 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -636 kJ                                        mol.sup.-1,                                              [II-427]                                                                           ZrO.sub.2 (cr) + 7F*(g) → ZrF.sub.3 (cr) + 2OF.sub.2 (g)            -1097   7 × 245                                                                       -1402                                                                              2 × 24,                                                                       ΔH.sub.r *(298 K.) = -1972 kJ mol.sup.-1,          [II-428]                                                                           ZrO.sub.2 (cr) + 8F(g) → ZrF.sub.4 (cr) + 2OF.sub.2 (g)             -1097   8 × 79                                                                        -1911                                                                              2 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1398 kJ                                       mol.sup.-1                                               -1040   8 × 62                                                                        -1810                                                                              2 × 42,                                                                       ΔG.sub. r.sup.0 (298 K.) = -1182 kJ                                      mol.sup.-1,                                              [II-429]                                                                           ZrO.sub.3 (cr) + 9F(g) → ZrF.sub.3 (cr) + 3OF.sub.2 (g)             -1008   9 × 79                                                                        -1402                                                                              3 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1033 kJ                                       mol.sup.-1,                                              [II-430]                                                                           ZrO.sub.3 (cr) + 9F*(g) → ZrF.sub.3 (cr) + 3OF.sub.2 (g)            -1008   9 × 245                                                                       -1402                                                                              3 × 24,                                                                       ΔH.sub.r *(298 K.) = -2527 kJ mol.sup.-1           and                                                                            [II-431]                                                                           ZrO.sub.3 (cr) + 10F(g) → ZrF.sub.4 (cr) + 3OF.sub.2 (g)            -1008   10 × 79                                                                       -1911                                                                              3 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1621 kJ                 __________________________________________________________________________                           mol.sup.-1.                                         

Thus, excited state monofluorine will remove the oxides by way of the trifluoride, and ground state monofluorine will remove the oxides by way of the tetrafluoride.

    __________________________________________________________________________     [II-432]                                                                           ZrCl.sub.2 (cr) + 9F(g) → ZrF.sub.3 (cr) + 2ClF.sub.3 (g)           -431    9 × 79                                                                        -1402                                                                              2 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2000 kJ                                       mol.sup.-1,                                             -386    9 × 62                                                                        -1326                                                                              2 × -119,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1736 kJ                                       mol.sup.-1                                              [II-433]                                                                           ZrCl.sub.3 (cr) + 12F(g) → ZrF.sub.3 (cr) + 3ClF.sub.3 (g)          -714    12 × 79                                                                       -1402                                                                              3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2113 kJ                                       mol.sup.-1                                              -646    12 × 62                                                                       -1326                                                                              3 × -119,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1781 kJ                                       mol.sup.-1,                                             [II-434]                                                                           ZrCl.sub.4 (cr) + 15F(g) → ZrF.sub.3 (cr) + 4ClF.sub.3 (g)          -981    15 × 79                                                                       -1402                                                                              4 ×  -159,                                                                     ΔH.sub.r.sup.0 (298 K.) = -2242 kJ                                       mol.sup.-1                                              -890    15 × 62                                                                       -1326                                                                              4 × -119,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1842 kJ                                       mol.sup.-1                                              and                                                                            [II-435]                                                                           ZrH.sub.2 (cr) + 5F(g) → ZrF.sub.3 (cr) + 2HF(g)                    -169    5 × 79                                                                        -1402                                                                              2 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2172 kJ                                       mol.sup.-1                                              -129    5 × 62                                                                        -1326                                                                              2 × -275,                                                                      ΔG.sub.r.sup.0 (298 K.) = -2057 kJ                                       mol.sup.-1,                                             [II-436]                                                                           ZrO.sub.2 (cr) + 6H(g) → ZrH.sub.2 (cr) + 2H.sub.2 O(g)             -1097   6 × 218                                                                       -169                                                                               2 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -864 kJ                                        mol.sup.-1                                              -1040   6 × 203                                                                       -129                                                                               2 × -229,                                                                      ΔG.sub.r.sup.0 (298 K.) =  -765 kJ                                       mol.sup.-1,                                             [II-437]                                                                           ZrO.sub.3 (cr) + 8H(g) → ZrH.sub.2 (cr) + 3H.sub.2 O(g)             -1008   8 × 218                                                                       -169                                                                               3 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1631 kJ                                       mol.sup.-1,                                             [II-438]                                                                           ZrCl.sub.2 (cr) + 4H(g) → ZrH.sub.2 (cr) + 2HCl(g)                  -431    4 × 218                                                                       -169                                                                               2 × -92,                                                                       ΔH.sub.r.sup.0 (298 K.) = -794 kJ                                        mol.sup.-1                                              -386    4 × 203                                                                       -129                                                                               2 × -95,                                                                       ΔG.sub.r.sup.0 (298 K.) = -745 kJ                                        mol.sup.-1,                                             [II-439]                                                                           ZrCl.sub.3 (cr) + 5H(g) → ZrH.sub.2 (cr) + 3HCl(g)                  -714    5 × 218                                                                       -169                                                                               3 × -92,                                                                       ΔH.sub.r.sup.0 (298 K.) = -821 kJ                                        mol.sup.-1                                              -646    5 × 203                                                                       -129                                                                               3 × -95,                                                                       ΔG.sub.r.sup.0 (298 K.) = -783 kJ                                        mol.sup.-1,                                             [II-440]                                                                           ZrCl.sub.4 (cr) + 6H(g) → ZrH.sub.2 (cr) + 4HCl(g)                  -981    6 × 218                                                                       -169                                                                               4 × -92,                                                                       ΔH.sub.r.sup.0 (298 K.) = -864 kJ                                        mol.sup.-1                                              -890    6 × 203                                                                       -129                                                                               4 × -95,                                                                       ΔG.sub.r.sup.0 (298 K.) = -837 kJ                                        mol.sup.-1,                                             [II-441]                                                                           ZrF.sub.2 (cr) + 4H(g) → ZrH.sub.2 (cr) + 2HF(g)                    -962    4 × 218                                                                       -169                                                                               2 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -623 kJ                                        mol.sup.-1                                              -913    4 × 203                                                                       -129                                                                               2 × -275,                                                                      ΔG.sub.r.sup.0 (298 K.) = -578 kJ                                        mol.sup.-1,                                             [II-442]                                                                           ZrF.sub.3 (cr) + 5H(g) → ZrH.sub.2 (cr) + 3HF(g)                    -1402    5 × 218                                                                      -169                                                                               3 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -673 kJ                                        mol.sup.-1                                              -1326   5 × 203                                                                       -129                                                                               3 × -275,                                                                      ΔG.sub.r.sup.0 (298 K.) = -643 kJ                                        mol.sup.-1                                              and                                                                            [II-443]                                                                           ZrF.sub.4 (cr) + 6H(g) → ZrH.sub.2 (cr) + 4HF(g)                    -1911   6 × 218                                                                       -168                                                                               4 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -653 kJ                                        mol.sup.-1                                              -1810   6 × 203                                                                       -129                                                                               4 × -275,                                                                      ΔG.sub.r.sup.0 (298 K.) = -637 kJ                 __________________________________________________________________________                            mol.sup.-1.                                        

Thus, we have the choice of three procedures for the volatilization of zirconium species:

0 +F

H+F

F+(in the absence of ZrF₄).

4. HAFNIUM

The paucity of thermodynamic data on hafnium species precludes the extensive analyses which are possible for titanium and zirconium. It is, however, well known that zirconium and hafnium are quite similar in their chemistries. This can be seen by comparing the available thermodynamic data for hafnium with those of zirconium. Consider a given datum for hafnium from which has been subtracted the corresponding datum for zirconium. The difference varies from +4 kJ mol⁻¹ (gaseous MF₄) to -57 kJ mol⁻¹ (crystalline MO₂) for the enthalpies of formation. The average for the absolute values for the difference is 19 kJ mol⁻¹. If we assumed that this difference applies to the dihydride, then

    ΔH.sub.ƒ.sup.0 (HfH.sub.2 (cr), 298K)=-169±19kJ mol.sup.-1.

We shall use the value -188 kJ mol⁻¹ when HfH₂ is a reactant and -150 kJ mol⁻¹ when it is a product.

    __________________________________________________________________________     [II-444]                                                                           Hf(cr) + O(g) → HfO(g)                                              0       249  50,      ΔH.sub.r.sup.0 (298 K.) = -199 kJ                                        mol.sup.-1,                                              [II-445]                                                                           Hf(cr) + 2O(g) → HfO.sub.2 (cr)                                     0       2 × 249                                                                       -1145,   ΔH.sub.r.sup.0 (298 K.) = -1643 kJ                                       mol.sup.-1                                               0       2 × 232                                                                       -1088, ΔG.sub.r.sup.0 (298 K.) = -1552 kJ mol.sup.-1,       [II-446]                                                                           HfCl.sub.4 (cr) + 10O(g) → HfO.sub.2 (cr) + 4ClO.sub.2 (g)          -990    10 × 249                                                                      -1145                                                                              4 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2237 kJ                                       mol.sup.-1                                               -901    10 × 232                                                                      -1088                                                                              4 × 120, ΔG.sub.r.sup.0 (298 K.) = -2027 kJ                        mol.sup.-1,                                                   [II-447]                                                                           HfF.sub.4 (cr) + 10O(g) → HfO.sub.2 (cr) + 4FO.sub.2 (g)            - 1930  10 × 249                                                                      -1145                                                                              4 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1653 kJ                                       mol.sup.-1                                               -1830   10 × 232                                                                      -1088                                                                              4 × 27, ΔG.sub.r.sup.0 (298 K.) = -1470 kJ                         mol.sup.-1,                                                   and                                                                            [II-448]                                                                           HfH.sub.2 (cr) + 3O(g) → HfO.sub.2 (cr) + H.sub.2 O(g)              -188    3 × 249                                                                       -1145                                                                              -242,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1946 kJ                                       mol.sup.-1,                                              [II-449]                                                                           Hf(cr) + 4F(g) → HfF.sub.4 (cr)                                     0       4 × 79                                                                        -1930,   ΔH.sub.r.sup.0 (298 K.) = -2246 kJ                                       mol.sup.-1                                               0       4 × 62                                                                        -1830, ΔG.sub.r.sup.0 (298 K.) = -2078 kJ mol.sup.-1,       [II-450]                                                                           HfO.sub.2 (cr) + 8F(g) → HfF.sub.4 (cr) + 2OF.sub.2 (g)             -1145   8 × 79                                                                         -1930                                                                             2 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1369 kJ                                       mol.sup.-1                                               -1088   8 × 62                                                                        -1830                                                                              2 × 42, ΔG.sub.r.sup.0 (298 K.) = -1154 kJ                         mol.sup.-1,                                                   [II-451]                                                                           HfCl.sub.4 (cr) + 16F(g) → HfF.sub.4 (cr) + 4ClF.sub.3 (g)          -990    16 × 79                                                                       -1930                                                                              4 × -159,                                                                     ΔH.sub.r.sup.0 (298 K.) = -2840 kJ                                       mol.sup.-1                                               -901    16 × 62                                                                       -1830                                                                              4 × -119, ΔG.sub.r.sup.0 (298 K.) = -2397 kJ                       mol.sup.-1                                                    and                                                                            [II-452]                                                                           HfH.sub.2 (cr) + 6F(g) → HfF.sub.4 (cr) + 2HF(g)                    -188    6 × 79                                                                        -1930                                                                              2 × -272,                                                                     ΔH.sub.r.sup.0 (298 K.) = -2760 kJ                 __________________________________________________________________________                           mol.sup.-1                                          

Since the `times four` criterion for the volatilization of hafnium tetrafluoride is 1040 kJ mol⁻¹, monofluorine clearly is an effective volatilizing reagent for these hafnium species.

    __________________________________________________________________________     [II-453]                                                                           Hf(cr) + 2H(g) → HfH.sub.2 (cr)                                     0       2 × 218                                                                       -150,     ΔH.sub.r.sup.0 (298 K.) = -586 kJ                                        mol.sup.-1,                                             [II-454]                                                                           HfO.sub.2 (cr) + 6H(g) → HfH.sub.2 (cr) + H.sub.2 O(g)              -1145   6 × 218                                                                       -150                                                                               2 × -242,                                                                      ΔH.sub.r.sup.0 (298 K.) = -797 kJ                                        mol.sup.-1,                                             [II-455]                                                                           HfCl.sub.4 (cr) + 6H(g) → HfH.sub.2 (cr) + 4HCl(g)                  -990    6 × 218                                                                       -150                                                                               4 × -92,                                                                       ΔH.sub.r.sup.0 (298 K.) = -836 kJ                                        mol.sup.-1                                              and                                                                            [II-456]                                                                           HfF.sub.4 (cr) + 6H(g) → HfH.sub.2 (cr) + 4HF(g)                    -1930   6 × 218                                                                       -150                                                                               4 × -272,                                                                      ΔH.sub.r.sup.0 (298 K.) = -616 kJ mol.sup.-                              1.                                                      __________________________________________________________________________

As was the case for titanium and zirconium we have the choice of three procedures for the volatilization of hafnium species:

O+F

H+F

F (in the absence of HfF₄).

L. Group V B.

By the criterion of [II-1] VF₅ (l) will volatilize spontaneously in the Apparatus. By the criterion of [II-2] VCl₄ (l), NbF₅ (cf), TaCl₅ (cf) and (CH₃)₅ Ta(l) will volatilize spontaneously in the Apparatus. Furthermore, the enthalpy of sublimation of niobium pentafluoride is 74 kJ mol⁻¹ with a `times four` criterion of 296 kJ mol¹.

Since we do not know the enthapy of formation of tantalum tetrafluoride, we cannot calculate the `times four` criterion for it. We note, however,

    ______________________________________                                         SPECIES        M.P. (°C.)                                                                        B.P. (°C.)                                     ______________________________________                                         VF.sub.5       19.5      47.9                                                  NbF.sub.5      76        225                                                   TaF.sub.5      95-97     229                                                   ______________________________________                                          (Ref. <II26>).                                                           

                  TABLE II-15                                                      ______________________________________                                         GROUP VB                                                                       THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES  V           Nb          Ta                                            ______________________________________                                         MO(cr)   -432/-404   -420/-392   +192/+164                                     (l)      -371/-352   -337/-320                                                 (g)      +128/+98    +199/+169   +251a/+222a                                   M.sub.2 O.sub.3 (cr)                                                                    -1219/-1139                                                           (l)      -1093/-1029                                                           MO.sub.2 (cr)                                                                           -714/-659   -795/-739                                                 (l)      -666/-662   -711/-667                                                 (g)      -233/-232   -200/-209   -201/-211                                     M.sub.2 O.sub.5 (cr)                                                                    -1551/-1419 -1900/-1766 -2046/-1911                                   (l)      -1491/-1378 -1831/-1707 -1957/-1834                                   MCl.sub.2 (cr)                                                                          -452a/-406a                                                           (g)      -256a/--                                                              MCl.sub.3 (cr)                                                                          -581a/-511a -360a/--    -533a/--                                      MCl.sub.4 (cr)       -694a/--    -702a/--                                      (l)      -569a/-504a                                                           (g)      -526a/-492a 561a/--     561a/--                                       MCl.sub. 5 (cr)      -797/-684   -858/-746                                     (l)                  -773/-674   -834/-736                                     (g)                              -765/-709                                     MF.sub.4 (cr)                                                                           -1403a/--                                                             MF.sub.5 (cr)        -1814/-1699 -1904a/--                                     (l)      -1480a/-1373a                                                         (g)      -1434a/-1370a                                                                              -1740/-1674                                               M(CO).sub.6 (g)                                                                         -987a/--                                                              (CH.sub.3).sub.5 M(l)            +170b/--                                      (g)                              +212b/--                                      ______________________________________                                          (a, Ref. <B>, b, Ref. <II15>).                                           

Since the data for the niobium and tantalum pentafluorides, are rather close, we can safely assume that the `times four` criterion is less than 600 kJ mol⁻¹.

2. VANADIUM

    __________________________________________________________________________     [II-457]                                                                           V(cr) + O(g) → VO(cr)                                               0          249   -432,  ΔH.sub.r.sup.0 (298 K.) = -681 kJ                                        mol.sup.-1                                             0          232   -404,  ΔG.sub.r.sup.0 (298 K.) = -336 kJ                                        mol.sup.-1,                                            [II-458]                                                                           VO(cr) + 0.5O(g) → 0.5V.sub.2 O.sub.3 (cr)                          -432       0.5 × 249                                                                      0.5 × -1219,                                                                    ΔH.sub.r.sup.0 (298 K.) = -302 kJ                                        mol.sup.-1                                             -404       0.5 × 232                                                                      0.5 × -1139,                                                                    ΔG.sub.r.sup.0 (298 K.) = -282 kJ                                        mol.sup.-1,                                            [II-459]                                                                           0.5V.sub.2 O.sub.3 (cr) + 0.5O(g) → VO.sub.2 (cr)                   0.5 × -1219                                                                         0.5 × 249                                                                      -714,  ΔH.sub.r.sup.0 (298 K.) = -229 kJ                                        mol.sup.-1                                             0.5 × -1139                                                                         0.5 × 232                                                                      -659,  ΔG.sub.r.sup.0 (298 K.) = -206 kJ                                        mol.sup.-1                                              and                                                                           [II-460]                                                                           VO.sub.2 (cr) + 0.5O(g) → 0.5V.sub.2 O.sub.5 (cr)                   -714       0.5 × 249                                                                      0.5 × -1551,                                                                    ΔH.sub.r.sup.0 (298 K.) = -186 kJ                                        mol.sup.-1                                             -659       0.5 × 232                                                                      0.5 × -1419,                                                                    ΔG.sub.r.sup.0 (298 K.) = -166 kJ                                        mol.sup.-1.                                            __________________________________________________________________________

The enthalpy of melting of the monoxide is 61 kJ mol⁻¹ with a `times four` criterion of 244 kJ mol⁻¹. Thus, the product of [II-457] will be the liquid. The enthalpy of melting of divanadium trioxide is 126 kJ mol⁻¹ with a `times four` criterion of 504 kJ mol⁻¹. For one-half mole, therefore, the criterion is 252 kJ mol⁻¹, and the product of [II-458] is the liquid.

For the dioxide the enthalpy of melting is 48 kJ mol⁻¹ with a `times four` criterion of 192 kJ mol⁻¹, and the product of [II-459] is the liquid. The enthalpy of melting of divanadium pentoxide is 60 kJ mol⁻¹ with a `times four` criterion of 240 kJ mol⁻¹. For one-half mole, therefore, the criterion is 120 kJ mol⁻¹, and the product of [II-460] is the liquid.

The reaction of monoxygen with a solid may yield only a surface `skin` of oxide. With a liquid the reaction will go to completion. Thus, for any sufficiently exothermic reaction with monoxygen the product will be divanadium pentoxide.

    __________________________________________________________________________     [II-461]                                                                           VCl.sub.2 (cr) + 6.5O(g) → 0.5V.sub.2 O.sub.5 (cr)                      + 2ClO.sub.2 (g)                                                           -452    6.5 × 249                                                                      0.5 × -1551                                                                     2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1738 kJ                                       mol.sup.-1                                           -406    6.5 × 232                                                                      0.5 × -1419                                                                     2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1572 kJ                                       mol.sup.-1,                                          [II-462]                                                                           VCl.sub.3 (cr) + 8.5O(g) → 0.5V.sub.2 O.sub.5 (cr)                      + 3ClO.sub.2 (g)                                                           -581    8.5 × 249                                                                      0.5 × -1551                                                                     3 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2005 kJ                                       mol.sup.-1                                           -511    8.5 × 232                                                                      0.5 × -1419                                                                     3 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1810 kJ                                       mol.sup.-1                                           and                                                                            [II-463]                                                                           VF.sub.4 (cr) + 10.5O(g) → 0.5V.sub.2 O.sub.5 (cr) + 4FO.sub.2          (g)                                                                        -1403   10.5 × 249                                                                     0.5 × -1551                                                                     4 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1935 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

Thus, monoxygen will convert all of the halides to the molten divanadium pentoxide which will solidify at the end of the reaction.

    ______________________________________                                         [II-464]                                                                             V(cr) + F(g) → VF.sub.4 (cr)                                      0        4 × 79                                                                           -1403,  ΔH.sub.r.sup.0 (298 K.) = -1719 kJ                                       mol.sup.-1                                            and                                                                            [II-465]                                                                             VF.sub.4 (cr) + F(g) → VF.sub.5 (l)                               -1403    79      -1480,  ΔH.sub.r.sup.0 (298 K.) = -156 kJ                                        mol.sup.-1.                                           ______________________________________                                    

Thus, any reaction with monofluorine which produces the tetrafluoride will proceed further to produce the liquid pentafluoride. As noted above the pentafluoride will spontaneously vaporize in the Apparatus.

    __________________________________________________________________________     [II-466]                                                                           VO(cr) + 7F(g) → VF.sub.5 (l) + OF.sub.2 (g)                        -432    7 × 79                                                                        -1480 24,   ΔH.sub.r.sup.0 (298 K.) = -1577 kJ                                       mol.sup.-1                                            -404    7 × 62                                                                        -1373 42, ΔG.sub.r.sup.0 (298 K.) = -1361 kJ                                   mol.sup.-1,                                                 [II-467]                                                                           V.sub.2 O.sub.3 (cr) + 16F(g) → 2VF.sub.5 (l) + 3OF.sub.2 (g)       -1219   16 × 79                                                                       2 × -1480                                                                      3 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -2933 kJ                                       mol.sup.-1                                            -1139   16 × 62                                                                       2 × -1373                                                                      3 × 42, ΔG.sub.r.sup.0 (298 K.) = -2473 kJ                         mol.sup.-1,                                                 [II-468]                                                                           VO.sub.2 (cr) + 9F(g) → VF.sub.5 (l) + 2OF.sub.2 (g)                -714    9 × 79                                                                        -1480 2 × 24,                                                                        Δ H.sub.r.sup.0 (298 K.) = -1429 kJ                                      mol.sup.-1                                            -659    9 × 62                                                                        -1373 2 × 42, ΔG.sub.r.sup.0 (298 K.) = -1188 kJ                         mol.sup.-1,                                                 [II-469]                                                                           V.sub.2 O.sub.5 (cr) + 20F(g) → 2VF.sub.5 (l) + 5OF.sub.2 (g)       -1551   20 × 79                                                                       2 × -1480                                                                      5 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -2869 kJ                                       mol.sup.-1                                            -1419   20 × 62                                                                       2 × -1373                                                                      5 × 42, ΔG.sub.r.sup.0 (298 K.) = -2357 kJ                         mol.sup.-1,                                                 [II-470]                                                                           VCl.sub.2 (cr) + 11F(g) → VF.sub.5 (l) + 2ClF.sub.3 (g)             -452    11 × 79                                                                       -1480 2 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2215 kJ                                       mol.sup.-1                                            -406    11 × 62                                                                       -1373 2 × -119, ΔG.sub.r.sup.0 (298 K.) =  -1887                         kJ mol.sup.-1                                               and                                                                            [II-471]                                                                           VCl.sub.3 (cr) + 14F(g) → VF.sub.5 (l) + 3ClF.sub.3 (g)             -581    14 × 79                                                                       -1480 3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2482 kJ                                       mol.sup.-1                                            -511    14 × 62                                                                       -1373 3 × -119, ΔH.sub.r.sup.0 (298 K.) = -2087                          kJ mol.sup.-1.                                              __________________________________________________________________________

Thus, both O+F and F are effective procedures for the volatilization of vanadium species.

Since vanadium hexacarbonyl is a highly volatile compound, it is worth investigating whether carbon monoxide is an effective volatilizing reagent for vanadium species.

    __________________________________________________________________________     [II-472]                                                                           V(cr) + 6CO(g) → V(CO).sub.6 (g)                                    0       6 × -111                                                                       -987,       ΔH.sub.r.sup.0 (298 K.) = -1653 kJ                                       mol.sup.-1,                                          [II-473]                                                                           VO(cr) + 7CO(g) → V(CO).sub.6 (g) + CO.sub.2 (g)                    -432    7 × -111                                                                       -987  -394, ΔH.sub.r.sup.0 (298 K.) = -1726 kJ                                       mol.sup.-1,                                          [II-474]                                                                           V.sub.2 O.sub.3 (cr) + 15CO(g) → 2V(CO).sub.6 (g) + 3CO.sub.2           (g)                                                                        -1219   15 × -111                                                                      2 × -987                                                                       3 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3602 kJ                                       mol.sup.-1,                                          [II-475]                                                                           VO.sub.2 (cr) + 8CO(g) → V(CO).sub.6 (g) + 2CO.sub.2 (g)            -714    8 × -111                                                                       -987  2 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1949 kJ                                       mol.sup.-1,                                          [II-476]                                                                           V.sub.2 O.sub.5 + 17CO(g) → 2V(CO).sub.6 (g) + 5CO.sub.2 (g)        -1551   17 × -111                                                                      2 × -987                                                                       5 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -4280 kJ                                       mol.sup.-1                                           [II-477]                                                                           VCl.sub.2 (cr) + 8CO(g) → V(CO).sub.6 (g) + 2COCl(g)                -452    8 × -111                                                                       -987  2 × 63,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1594 kJ                                       mol.sup.-1                                           [II-478]                                                                           VCl.sub.3 (cr) + 9CO(g) → V(CO).sub.6 (g) + 3COCl(g)                -581    9 × -111                                                                       -987  3 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1594 kJ                                       mol.sup.-1                                           and                                                                            [II-479]                                                                           VF.sub.4 (cr) + 10CO(g) → V(CO).sub.6 (g) + 4COF(g)                 -1403   10 × - 111                                                                     -987  4 × -172,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1382 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

Thus, we have the choice of four procedures for the volatilization of vanadium species:

O+F

O+CO

CO

3. NIOBIUM

    __________________________________________________________________________     [II-480]                                                                           Nb(cr) + O(g) → NbO(cr)                                             0       249   -420,  ΔH.sub.r.sup.0 (298 K.) = -669 kJ mol.sup.-1        0       232   -392, ΔG.sub.r.sup.0 (298 K.) = -595 kJ mol.sup.-1,        [II-481]                                                                           NbO(cr) + O(g) → NbO.sub.2 (g)                                      -420    249   -795,  ΔH.sub.r.sup.0 (298 K.) = -624 kJ mol.sup.-1        -392    232   -739,  ΔG.sub.r.sup.0 (298 K.) = -579 kJ mol.sup.-1,       and                                                                            [II-482]                                                                           NbO.sub.2 (cr) + 0.5O(g) → 0.5Nb.sub.2 O.sub.5 (cr)                 -795    0.5 × 249                                                                      0.5 × -1900,                                                                    ΔH.sub.r.sup.0 (298 K.) = -280 kJ mol.sup.-1        -739    0.5 × 232                                                                      0.5 × -1766,                                                                    ΔG.sub.r.sup.0 (298 K.) = -260 kJ                   __________________________________________________________________________                          mol.sup.-1.                                          

The enthalpy of melting of the monoxide is 83 kJ mol⁻¹ with a `times four ` criterion of 332 kJ mol⁻¹. Thus, the product of [II-480] will be the liquid. For the dioxide the enthalpy of melting is 84 kJ mol⁻¹ with a `times four` criterion of 336 kJ mol⁻¹, and the product of [II-481] will be the liquid. The enthalpy of melting of diniobium pentoxide is 69 kJ mol⁻¹ with a `times four` criterion of 276 kJ mol⁻¹. For one-half mole, therefore, the criterion is 138 kJ mol⁻¹, and the product of [II-482] is the liquid.

    __________________________________________________________________________     [II-483]                                                                           NbCl.sub.3 (cr) + 8.5O(g) → 0.5Nb.sub.2 O.sub.5 (cr) +                  3ClO.sub.2 (g)                                                             -360    8.5 × 249                                                                      0.5 × -1900                                                                     3 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2400 kJ                                       mol.sup.-1,                                          [II-484]                                                                           NbCl.sub.4 (cr) + 10.5O(g) → 0.5Nb.sub.2 O.sub.5 (cr) +                 4ClO.sub.2 (g)                                                             -694    10.5 × 249                                                                     0.5 × -1900                                                                     4 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2462 kJ                                       mol.sup.-1,                                          [II-485]                                                                           NbCl.sub.5 (cr) + 12.5O(g) → 0.5Nb.sub.2 O.sub.5 (cr) +                 5ClO.sub.2 (g)                                                             -797    12.5 × 249                                                                     0.5 × -1900                                                                     5 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2756 kJ                                       mol.sup.-1                                           -684    12.5 × 232                                                                     0.5 × 1766                                                                      5 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -2499 kJ                                       mol.sup.-1                                           and                                                                            [II-486]                                                                           NbF.sub.5 (cr) + 12.5O(g) → 0.5Nb.sub.2 O.sub.5 (cr) +                  5FO.sub.2 (g)                                                              -1814   12.5 × 249                                                                     0.5 × -1900                                                                     5 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2128 kJ                                       mol.sup.-1                                           -1699   12.5 × 232                                                                     0.5 × -1766                                                                     5 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1874 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

Thus, monoxygen will convert all of the halides to the molten diniobium pentoxide which will solidify at the end of the reaction.

    __________________________________________________________________________     [II-487]                                                                           Nb(cr) + 5F(g) → NbF.sub.5 (cr)                                     0       5 × 79                                                                        -1814,      ΔH.sub.r.sup.0 (298 K.) = -2209 kJ                                       mol.sup.-1                                            0       5 × 62                                                                        -1699,      ΔG.sub.r.sup.0 (298 K.) = -2009 kJ                                       mol.sup.-1,                                           [II-488]                                                                           NbO(cr) + 7F(g) → NbF.sub.5 (cr) + OF.sub.2 (g)                     -420    7 × 79                                                                        -1814 24,   ΔH.sub.r.sup.0 (298 K.) = -1923 kJ                                       mol.sup.-1                                            -392    7 × 62                                                                        -1699 42,   ΔG.sub.r.sup.0 (298 K.) = -1699 kJ                                       mol.sup.-1,                                           [II-489]                                                                           NbO.sub.2 (cr) + 9F(g) → NbF.sub.5 (cr) + 2OF.sub.2 (g)             -795    9 × 79                                                                        -1814 2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1682 kJ                                       mol.sup.-1                                            -739    9 × 62                                                                        -1699 2 × 42,                                                                        Δ G.sub.r.sup.0 (298 K.) = -1434 kJ                                      mol.sup.-1,                                           [II-490]                                                                           Nb.sub.2 O.sub.5 (cr) + 20F(g) → 2NbF.sub.5 (cr) + 5OF.sub.2            (g)                                                                        -1900   20 × 79                                                                       2 × -1814                                                                      5 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -3188 kJ                                       mol.sup.-1                                            -1716   20 × 62                                                                       2 × -1699                                                                      5 × 42,                                                                        ΔG.sub.r.sup.0 (298 K.) = -2662 kJ                                       mol.sup.-1,                                           [II-491]                                                                           NbCl.sub.3 (cr) + 14F(g) → NbF.sub.5 (cr) + 3ClF.sub.3 (g)          -360    14 × 79                                                                       -1814 3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3037 kJ                                       mol.sup.-1                                            and                                                                            [II-492]                                                                           NbCl.sub.5 (cr) + 20F(g) → NbF.sub.5 (cr) + 5ClF.sub.3 (g)          -797    20 × 79                                                                       -1814 5 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -3392 kJ                                       mol.sup.-1                                            -684    20 × 62                                                                       -1699 5 × -119,                                                                      ΔG.sub.r.sup.0 (298 K.) = -2850 kJ                                       mol.sup.-1.                                           __________________________________________________________________________

Thus, we have the choice of two procedures for the volatilization of niobium species:

O+F

4. TANTALUM

    ______________________________________                                         [II-493]                                                                             Ta(cr) + O(g) → TaO(cr)                                           0        249     192, ΔH.sub.r.sup.0 (298 K.) = -57 kJ mol.sup.-1        0        203     164, ΔG.sub.r.sup.0 (298 K.) = -39 kJ mol.sup.-1,       and                                                                            [II-945]                                                                             TaO(cr) + 1.5O(g) → 0.5Ta.sub.2 O.sub.5 (cr)                      192       1.5 × 249                                                                           0.5 × -2046, ΔH.sub.r.sup.0 (298 K.) =                             -1588 kJ mol.sup.-1                                       164       1.5 × 203                                                                           0.5 × -1911, ΔG.sub.r.sup.0 (298 K.) =                             -1424 kJ mol.sup.-1.                                      ______________________________________                                    

The enthalpy of melting of ditantalum pentoxide is 89 kJ mol⁻¹ with a `times four` criterion of 356 kJ mol⁻¹.

    __________________________________________________________________________     [II-495]                                                                           TaCl.sub.3 (cr) + 8.5O(g) → 0.5Ta.sub.2 O.sub.5 (cr) +                  3ClO.sub.2 (g)                                                             -553    8.5 × 249                                                                      0.5 × -2046                                                                     3 × 102, ΔH.sub.r.sup.0 (298 K.) = -2280                           kJ mol.sup.-1,                                            [II-496]                                                                           TaCl.sub.4 (cr) + 10.5O(g) → 0.5Ta.sub.2 O.sub.5 (cr) +                 4ClO.sub.2 (g)                                                             -702    10.5 × 249                                                                     0.5 × -2046                                                                     4 × 102, ΔH.sub.r.sup.0 (298 K.) = -2528                           kJ mol.sup.-1,                                            [II-497]                                                                           TaCl.sub.5 (cr) + 12.5O(g) → 0.5Ta.sub.2 O.sub.5 (cr) +                 5ClO.sub.2 (g)                                                             -858    12.5 × 249                                                                     0.5 × -2046                                                                     5 × 102, ΔH.sub.r.sup.0 (298 K.) = -2768                           kJ mol.sup.-1                                             -746    12.5 × 232                                                                     0.5 × -1911                                                                     5 × 120, ΔG.sub.r.sup.0 (298 K.) = -2510                           kJ mol.sup. -1                                            and                                                                            [II-498]                                                                           TaF.sub.5 (cr) + 12.5O(g) → 0.5Ta.sub.2 O.sub.5 (cr) +                  5FO.sub.2 (g)                                                              -1904   12.5 × 249                                                                     0.5 × -2046                                                                     5 × 13, ΔH.sub.r.sup.0 (298 K.) = -2166                            kJ mol.sup.-1.                                            __________________________________________________________________________

Thus, nonoxygen will convert all of the halides to ditantalum pentoxide.

    __________________________________________________________________________     [II-499]                                                                           Ta(cr) + 5(g) → TaF.sub.5 (cr)                                      0        5 × 79                                                                          -1904, ΔH.sub.r.sup.0 (298 K.) = -2299 kJ                                mol.sup.-1,                                                    [II-500]                                                                           TaO(cr) + 7F(g) → TaF.sub.5 (cr) + OF.sub.2 (g)                     192      7 × 79                                                                        -1904                                                                               24, ΔH.sub.r.sup.0 (298 K.) = -2625 kJ                                   mol.sup.-1,                                                 [II-501]                                                                           Ta.sub.2 O.sub.5 (cr) + 20F(g) → TaF.sub.5 (cr) + 5OF.sub.2             (g)                                                                        -2046    20 × 79                                                                       -1904                                                                              5 × 24, ΔH.sub.r.sup.0 (298 K.) = -1318 kJ                         mol.sup.-1,                                                  [II-502]                                                                           TaCl.sub.3 (cr) + 14F(g) → TaF.sub.5 (cr) + 3ClF.sub.3 (g)          -533    14 × 79                                                                       -1904                                                                              3 × -159, ΔH.sub.r.sup.0 (298 K.) = -2954 kJ                       mol.sup.-1,                                                   [II-503]                                                                            TaCl.sub.4 (cr) + 17F(g) → TaF.sub.5 (cr) + 4ClF.sub.3 (g)         -702    17 × 79                                                                       -1904                                                                              4 × -159, ΔH.sub.r.sup.0 (298 K.) = -3181 kJ                       mol.sup.-1                                                    and                                                                            [II-504]                                                                           TaCl.sub.5 (cr) + 20F(g) → TaF.sub.5 (cr) + 5ClF.sub.3 (g)          -858    20 × 79                                                                       -1904                                                                              5 × -159, ΔH.sub.r.sup.0 (298 K.) = -3421 kJ                       mol.sup.-1.                                                   __________________________________________________________________________

Thus, we see that with the monofluorine reactions there is no difficulty in meeting the assumed `times four` criterion for the volatilization of tantalum pentafluoride.

    __________________________________________________________________________     [II-505]                                                                           Ta(cr) + 5 CH.sub.3 (g) → (CH.sub.3).sub.5 Ta(l)                    0     5 × 146                                                                       170, ΔH.sub.r.sup.0 (298 K.) = .560 kJ mol.sup.-1,            [II-506]                                                                           TaO(cr) + 7 CH.sub.3 (g) → (CH.sub.3).sub.5 Ta(l)                       + (CH.sub.3).sub.2 O(g)                                                    192      7 × 146                                                                        170  -184, ΔH.sub.r.sup.0 (298 K.) = -1228 kJ                                       mol.sup.-1,                                          [II-507]                                                                           Ta.sub.2 O.sub.5 (cr) + 20 CH.sub.3 (g) → 2 (CH.sub.3).sub.5            Ta(l) + 5 (CH.sub.3).sub.2 O(g)                                            -2046    20 × 146                                                                       2 × 170                                                                       5 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1454 kJ                                       mol.sup.-1,                                          [II-508]                                                                           TaCl.sub.3 (cr) + 8 CH.sub.3 (g) → (CH.sub.3).sub.5 Ta(l) + 3           CH.sub.3 Cl(g)                                                             - 533    8 × 146                                                                        170  3 × -84,                                                                       ΔH.sub.r.sup.0 (298 K.) = -717 kJ                                        mol.sup.-1,                                          [II-509]                                                                           TaCl.sub.4 (cr) + 9 CH.sub.3 (g) → (CH.sub.3).sub.5 Ta(l) + 4           CH.sub.3 Cl(g)                                                             -702     9 × 146                                                                        170  4 × -84,                                                                       ΔH.sub.r.sup.0 (298 K.) = -778 kJ                                        mol.sup.-1,                                          [II-510]                                                                           TaCl.sub.5 (cr) + 10 CH.sub.3 (g) → (CH.sub.3).sub.5 Ta(l) + 5          CH.sub.3 Cl(g)                                                             -858     10 × 146                                                                       170  5 × -84,                                                                       ΔH.sub.r.sup.0 (298 K.) = -852 kJ                                        mol.sup.-1                                           and                                                                            [II-511]                                                                           TaF.sub.5 (cr) + 10 CH.sub.3 (g) → (CH.sub.3).sub.5 Ta(l) + 5           CH.sub.3 F(g)                                                              -1904    10 × 146                                                                       170  5 × -234,                                                                      ΔH.sub. r.sup.0 (298 K.) = .556 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

The enthalpy of vaporization of pentamethyltantalum is 42 kJ mol⁻¹ with a `times four` criterion of 168 kJ mol⁻¹. Thus, methyl is an effective volatilizing reagent for tantalum species. We, therefore, have the choice of four procedures for the volatilization of tantalum species:

O+F

F (in the absence of Ta F₅)

O+CH₃

CH₃.

M. Group VI B.

1. THERMODYNAMICS

                  TABLE II-16                                                      ______________________________________                                         GROUP VI B                                                                     THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.r.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES  Cr          Mo          W                                             ______________________________________                                         MO                                                                             (cr)                             -272b/--                                      (g)       +188/+155   +311/+278   +425/+391                                    M.sub.2 O.sub.3                                                                (cr)      -1135/-1053                                                          (l)       -1018/-950                                                           MO.sub.2                                                                       (cr)      -598a/--    -588/-532   -590/-534                                    (g)       -75a/-87a    -8/-21      +77/+62                                     MO.sub.3                                                                       (cr)      -590a/--    -745/-668   -842/-764                                    (l)                   -703/-638   -789/-718                                    (g)       -293/-273   -346/-331   -293/-277                                    MCl                               +553/+518                                    (g)                                                                            MCl.sub.2                                                                      (cr)      -395a/-356a                                                                                -282a/--    -257/-220                                    (g)       -128a/--                 -13/-29                                     MCl.sub.3                                                                      (cr)      -556a/-486a                                                                                -387a/--    -357b/--                                     (g)                               -37b/--                                      MCl.sub.4                                                                      (cr)                  -477/-402   -443/-359                                    (l)                   -463/-394                                                (g)       -427a/--    -384/-354   -336/-306                                    MCl.sub.5                                                                      (cr)                  -527/-423   -512/-402                                    (l)                   -510/-417   -495/-393                                    (g)                   -448/-391   -412/-357                                    MCl.sub.6                                                                      (cr)                  -523/-391   -594/-456                                    (l)                               -569/-445                                    (g)                   -439/-356   -494/-409                                    MF                    +283/+248   +386/+351                                    (g)                                                                            MF.sub.2                                                                       (cr)      -778a/--                -608b/--                                     (g)      -414a/--     -163/-175   -188b/--                                     MF.sub.3                                                                       (cr)     -1159a/                                                                        -1088a                                                                (g)                   -607/-596   -608b/--                                     MF.sub.4                                                                       (cr)     -1247a/--               -1208b/--                                     (g)                   -948/-916  -1030b/--                                     MF.sub.5                                                                       (cr)                             -1495b/--                                     (g)                   -1241/-1185                                                                               -1394b/--                                     MF.sub.6                                                                       (l)                   -1586/-1473                                                                                -1748/-1632                                  (g)                   -1558/-1472                                                                                -1722/-1632                                  M(CO).sub.6                                                                    (cr)     -1077a/--    -983/-878   -960b/--                                     (g)      -1006a/--    -912a/-856a                                                                                -884b/--                                     (CH.sub.3).sub.6 M                                                             (l)                               +739c/--                                     (g)                               +772c/--                                     ______________________________________                                          (a, Ref. <B>, b, Ref. <II27>, c, Ref. <II15>).                           

By the criterion of [II-1] MoF₆ (l), WF₆ (l) and MO(CO)₆ (cr) will volatilize spontaneously in the Apparatus. By Ref. <II-23> the enthalpy of sublimation of CrF₄ is 82 kJ mol⁻¹ with a `times four` criterion of 328 kJ mol⁻¹. The enthalpy of sublimation of Cr(CO)₆ is 71 kJ mol⁻¹ with a `times four` criterion of 284 kJ mol⁻¹.

The enthalpy of sublimation of WF₄ is 178 kJ mol⁻¹ with a `times four` criterion of 712 kJ mol⁻¹. The enthalpy of sublimation of WF₅ is 101 kJ mol⁻¹ with a `times four` criterion of 40 kJ mol⁻¹. For (W(CO)₆ the enthalpy of sublimation is 76 kJ mol⁻¹ with a `times four` criterion of 304 kJ mol⁻¹, and for (CH₃)₆ W the enthalpy of vaporization is 33 kJ mol⁻¹ with a `times four ` criterion of 132 kJ mol⁻¹.

2. CHROMIUM

    __________________________________________________________________________     [II-512]                                                                           Cr(cr) + O(g) → CrO(g)                                              0          249   188,   ΔH.sub.r.sup.0 (298 K.) = -61 kJ                                         mol.sup.-1                                             0          232   155,   ΔG.sub.r.sup.0 (298 K.) = -77 kJ                                         mol.sup.-1,                                            [II-513]                                                                           Cr(cr) + 1.5 O(g) → 0.5 Cr.sub.2 O.sub.3 (cr)                       0          1.5 × 249                                                                      0.5 × -1135,                                                                    ΔH.sub.r.sup.0 (298 K.) = -941 kJ                                        mol.sup.-1                                             0          1.5 × 232                                                                      0.5 × -1053,                                                                    ΔG.sub.r.sup.0 (298 K.) = -874 kJ                                        mol.sup.-1,                                            [II-514]                                                                           0.5 Cr.sub.2 O.sub.3 (cr) + 0.5 O(g) → CrO.sub.2 (cr)               0.5 × -1135                                                                         0.5 × 249                                                                      -598,  ΔH.sub.r.sup.0 (298 K.) = -155 kJ                                        mol.sup.-1                                             and                                                                            [II-515]                                                                           CrO.sub.2 (cr) + O(g) → CrO.sub.3 (cr)                              -598       249   -590,  ΔH.sub.r.sup.0 (298 K.) = -241 kJ                                        mol.sup.-1.                                            __________________________________________________________________________

The enthalpy of melting of the sesquioxide is 117 kJ mol⁻¹ with a `times four` criterion of 468 kJ mol⁻¹ (234 kJ/half mole). Thus, the product of [II-513] is actually the liquid. The enthalpy of sublimation of the trioxide is 297 kJ mol⁻¹ with a `times four` criterion of 1188 kJ mol⁻¹. Since

    ______________________________________                                         [II-516]                                                                             Cr(cr) + 3 O(g) → CrO.sub.3 (cr)                                  0       3 × 249                                                                            590, ΔH.sub.r.sup.0 (298 K.) = -1337 kJ                                  mol.sup.-1,                                                  ______________________________________                                    

monoxygen will volatilize chromium, but not the sesquioxide nor the dioxide.

    __________________________________________________________________________     [II-517]                                                                           CrCl.sub.2 (cr) + 7 O(g) → CrO.sub.3 (cr) + 2 ClO.sub.2 (g)         -395    7 × 249                                                                        -590                                                                               2 × 102, ΔH.sub.r.sup.0 (298 K.) = -1734 kJ                        mol.sup.-1,                                                  [II-518]                                                                           CrCl.sub.3 (cr) + 9 O(g) → CrO.sub.3 (cr) + 3 ClO.sub.2 (g)         -556    9 × 249                                                                        -590                                                                               3 × 102, ΔH.sub.r.sup.0 (298 K.) = -1969 kJ                        mol.sup.-1,                                                  [II-519]                                                                           CrF.sub.2 (cr) + 7 O(g) → CrO.sub.3 (cr) + 2 FO.sub.2 (g)           -778    7 × 249                                                                        -590                                                                                2 × 13, ΔH.sub.r.sup.0 (298 K.) = -1529 kJ                        mol.sup.-1,                                                  [II-520]                                                                           CrF.sub.3 (cr) + 9 O(g) → CrO.sub.3 (cr) + 3 FO.sub.2 (g)           -1159   9 × 249                                                                        -590                                                                                3 × 13, ΔH.sub.r.sup.0 (298 K.) = -1633 kJ                        mol.sup.-1                                                   and                                                                            [II-521]                                                                           CrF.sub.4 (cr) + 11 O(g) → CrO.sub.3 (cr) + 4 FO.sub.2 (g)          -1247   11 × 249                                                                       -590                                                                                4 × 13, ΔH.sub.r.sup.0 (298 K.) = -2030 kJ                        mol.sup.-1.                                                  __________________________________________________________________________

Thus, monoxygen is an effective volatilizing reagent for the halides. Since it is not an effective volatilizing reagent for the sesquioxide or the dioxide, monoxygen cannot be used by itself.

    ______________________________________                                         [II-522] Cr(cr) + 2 F(g) → CrF.sub.2 (cr)                                      0       2 × 79                                                                            -778, ΔH.sub.r.sup.0 (298 K.) =                                          -936 kJ mol.sup.-1,                                    [II-523] CrF.sub.2 (cr) + F(g) → CrF.sub.3 (cr)                                -778    79       -1159, ΔH.sub.r.sup.0 (298 K.) =                                         -460 kJ mol.sup.-1,                                    [II-524] CrF.sub.3 (cr) + F(g) → CrF.sub.4 (cr)                                -1159   79       -1247, ΔH.sub.r.sup.0 (298 K.) =                                         -167 kJ mol.sup.-1                                     and                                                                            [II-525] Cr(cr) + 4 F(g) → CrF.sub.4 (cr)                                      0       4 × 79                                                                            -1247, ΔH.sub.r.sup.0 (298 K.) =                                         -1563 kJ mol.sup.-1.                                   ______________________________________                                    

Since the `times four` criterion for the tetrafluoride is 328 kJ mol⁻¹, monofluorine is an effective exchange for chromium.

    __________________________________________________________________________     [II-526]                                                                           0.5 Cr.sub.2 O.sub.3 (cr) + 7 F(g) → CrF.sub.4 (cr) + 1.5               OF.sub.2 (g)                                                               0.5 × -1135                                                                         7 × 79                                                                          -1247                                                                              1.5 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1196 kJ                                       mol.sup.-1,                                       [II-527]                                                                           CrO.sub.2 (cr) + 8 F(g) → CrF.sub.4 (cr) + 2 OF.sub.2 (g)           -598       8 × 79                                                                          -1247                                                                              2 × 24,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1233 kJ                                       mol.sup.-1,                                       [II-528]                                                                           CrO.sub.3 cr) + 10 F(g) → CrF.sub.4 (cr) + 3 OF.sub.2 (g)           -590       10 × 79                                                                         -1247                                                                              3 × 24,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1375 kJ                                       mol.sup.-1,                                       [II-529]                                                                           CrCl.sub.2 (cr) + 10 F(g) → CrF.sub.4 (cr) + 2 ClF.sub.3 (g)        -395       10 × 79                                                                         -1247                                                                              2 × -159,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1960 kJ                                       mol.sup.-1                                        and                                                                            [II-530]                                                                           CrCl.sub.3 (cr) + 13 F(g) → CrF.sub.4 (cr) + 3 ClF.sub.3 (g)        -556       13 × 79                                                                         -1247                                                                              3 × -159,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2195 kJ                                       mol.sup.-1.                                       [II-531]                                                                           Cr(cr) + 6 CO(g) → Cr(CO.sub.6 (cr)                                 0          6 × -111                                                                        -1077, ΔH.sub.r.sup.0 (298 K.) = -411 kJ                                 mol.sup.-1,                                                  [II-532]                                                                           0.5 Cr.sub.2 O.sub.3 (cr) + 7.5 CO(g) → Cr(CO).sub.6 (cr) +             1.5 CO.sub.2 (g)                                                           0.5 × -1135                                                                         7.5 × -111                                                                      -1077                                                                              1.5 × -394,                                                                     ΔH.sub.r.sup.0 (298 K.) = -268 kJ                                        mol.sup.-1,                                       [II-533]                                                                           0.5 Cr.sub.2 O.sub. 3 (cr) + 7.5 CO*(g) → Cr(CO).sub.6 (cr) +           1.5 CO.sub.2 (g)                                                           0.5 × -1135                                                                         7.5 × 564                                                                       -1077                                                                              1.5 × -394,                                                                     ΔH.sub.r *(298 K.) = -5330 kJ                                            mol.sup.-1,                                       [II-534]                                                                           CrO.sub.2 (cr) + 8 CO(g) → Cr(CO).sub.6 (cr) + 2 CO.sub.2 (g)       -598       8 × -111                                                                        -1077                                                                              2 × -394,                                                                       ΔH.sub.r.sup.0 (298 K.) = -379 kJ                                        mol.sup.-1,                                       [II-535]                                                                           CrO.sub.3 (cr) + 9 CO(g) → Cr(CO).sub.6 (cr) + 3 CO.sub.2 (g)       -590       9 × -111                                                                        -1077                                                                              3 × -394,                                                                       ΔH.sub.r.sup.0 (298 K.) = -670 kJ                                        mol.sup.-1,                                       [II-536]                                                                           CrCl.sub.2 (cr) + 8 CO(g) → Cr(CO).sub.6 (cr) + 2 COCl(g)           -395       8 × -111                                                                        -1077                                                                               2 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +80 kJ                                         mol.sup.-1,                                       [II-537]                                                                           CrCl.sub.2 (cr) + 8 CO*(g) → Cr(CO).sub.6 (cr) + 2 COCl(g)          -395       8 × 564                                                                         -1077                                                                              2 × -63,                                                                        ΔH.sub.r *(298 K.) = -5320 kJ                                            mol.sup.-1,                                       [II-538]                                                                           CrCl.sub.3 (cr) + 9 CO(g) → Cr(CO).sub.6 (cr) + 3 COCl(g)           -556       9 × -111                                                                        -1077                                                                              3 × -63,                                                                        ΔH.sub.r.sup.0 (298 K.) = +289 kJ                                        mol.sup.-1,                                       [II-539]                                                                           CrCl.sub.3 (cr) + 9 CO*(g) → Cr(CO).sub.6 (cr) + 3 COCl(g)          -556       9 × 564                                                                         -1077                                                                              3 × -63,                                                                        ΔH.sub.r *(298 K.) = -5786 kJ                                            mol.sup.-1 ,                                      [II-540]                                                                           CrF.sub.2 (cr) + 8 CO(g) → Cr(CO).sub.6 (cr) +  2 COF(g)            -778       8 × -111                                                                        -1077                                                                              2 × -172,                                                                       ΔH.sub.r.sup.0 (298 K.) = +245 kJ                                        mol.sup.-1,                                       [II-541]                                                                           CrF.sub.2 (cr) + 8 CO*(g) → Cr(CO).sub.6 (cr) + 2 COF(g)            -778       8 × 564                                                                         -1077                                                                              2 × -172,                                                                       ΔH.sub.r.sup.0 (298 K.) = -5155 kJ                                       mol.sup.-1,                                       [II-542]                                                                           CrF.sub.3 (cr) + 9 CO(g) → Cr(CO).sub.6 (cr) + 3 COF(g)             -1159      9 × -111                                                                        -1077                                                                              3 × -172,                                                                       ΔH.sub.r.sup.0 (298 K.) = +565 kJ                                        mol.sup.-1,                                       [II-543]                                                                           CrF.sub.3 cr) + 9 CO*(g) → Cr(CO).sub.6 (cr) + 3 COF(g)             -1159      9 × 564                                                                         -1077                                                                              3 × -172,                                                                       ΔH.sub.r *(298 K.) = -5510 J                                             mol.sup.-1,                                        [II-544]                                                                          CrF.sub.4 cr) + 9 CO(g) → Cr(CO).sub.6 (cr) + 3 COF(g)              -1247      10 × -111                                                                       -1077                                                                              4 × -172,                                                                       ΔH.sub.r.sup.0 (298 K.) = +592 kJ                                        mol.sup.-1                                        and                                                                            [II-545]                                                                           CrF.sub.4 (cr) + 10 CO*(g) → Cr(CO).sub.6 (cr) + 4 COF(g)           -1247      10 × 564                                                                        -1077                                                                              4 × -172,                                                                       ΔH.sub.r *(298 K.) = -6158 kJ                                            mol.sup.-1.                                       __________________________________________________________________________

Since the `times four` criterion for chromium carbonyl is 284 kJ mol⁻¹, we have four choices for the procedure for volatilization of the chromium species:

O+F

F (in the absence of CrF₄)

O+CO

CO*.

3. MOLYBDENUM

The free energies of sublimation of the tetrachloride, the pentachloride and the hexachloride are 48, 32 and 35 kJ mol⁻¹, respectively. Since these values lie between the criteria of [II-1] and [II-2], these chlorides will sublime spontaneously in the Apparatus. Thus, in our analyses we need consider only the di- and tri-chlorides.

    ______________________________________                                         [II-546]                                                                             Mo(cr) + O(g) → MoO(g)                                            0        249      311, ΔH.sub.r.sup.0 (298 K.) = +62 kJ mol.sup.-1       0        232      278, ΔH.sub.r.sup.0 (298 K.) = +46 kJ                                    mol.sup.-1,                                                  [II-547]                                                                             Mo(cr) + 2 O(g) → MoO.sub.2 (cr)                                  0        2 × 249                                                                           -588, ΔH.sub.r.sup.0 (298 K.) = -1086 kJ                                 mol.sup.-1                                                   0        2 × 232                                                                           -532, ΔG.sub.r.sup.0 (298 K.) = -996 kJ                                  mol.sup.-1                                                   and                                                                            [II-548]                                                                             Mo(cr) + 3 O(g) → MoO.sub.3 (cr)                                  0        3 × 249                                                                           -745, ΔH.sub.r.sup.0 (298 K.) = -1492 kJ                                 mol.sup.-1                                                   0        3 × 232                                                                           -668, ΔG.sub.r.sup.0 (298 K.) = -1364 kJ                                 mol.sup.-1.                                                  ______________________________________                                    

The monoxide will not form. The dioxide will, but will not volatilize. If the trioxide is formed, it will be as the liquid which will then solidify.

    __________________________________________________________________________     [II-549]                                                                           MoCl.sub.2 (cr) + 6 O(g) → MoO.sub.2 (cr) + 2 ClO.sub.2 (g)         -282    6 × 249                                                                       -588                                                                               2 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1596 kJ                                       mol.sup.-1,                                             [II-550]                                                                           MoCl.sub.2 (cr) + 7 O(g) → MoO.sub.3 (cr) + 2 ClO.sub.2 (g)         -282    7 × 249                                                                       -745                                                                               2 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2002 kJ                                       mol.sup.-1,                                             [II-551]                                                                           MoCl.sub.3 (cr) + 8 O(g) → MoO.sub.2 (cr) + 3 ClO.sub.2 (g)         -387    8 × 249                                                                       -588                                                                               3 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1887 kJ                                       mol.sup.-1                                              and                                                                            [II-552]                                                                           MoCl.sub.3 (cr) + 9 O(g) → MoO.sub.3 (cr) + 3 ClO.sub.2 (g)         -387    9 × 249                                                                       -745                                                                               3 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2293 kJ                                       mol.sup.-1.                                             [II-553]                                                                           Mo(cr) + F(g) → MoF(g)                                              0     79   283, ΔH.sub.r.sup.0 (298 K.) = +204 kJ mol.sup.-1             0     62  248, ΔG.sub.r.sup.0 (298 K.) = +186 kJ mol.sup.-1,             [II-554]                                                                           Mo(cr) + 2 F(g) → MoF.sub.2 (g)                                     0     2 × 79                                                                       -163, ΔH.sub.r.sup.0 (298 K.) = -321 kJ mol.sup.-1             0     2 × 62                                                                       -175, ΔG.sub.r.sup.0 (298 K.) = -299 kJ mol.sup.-1,            [II-555]                                                                           Mo(cr) + 3 F(g) → MoF.sub.3 (g)                                     0     3 × 79                                                                       -607, ΔH.sub.r.sup.0 (298 K.) = -844 kJ mol.sup.-1             0     3 × 62                                                                       -596,ΔG.sub.r.sup.0 (298 K.) = -782 kJ mol.sup.-1,             [II-556]                                                                           MoO.sub.2 (cr) + 6 F(g) → MoF.sub.2 (g) + 2 OF.sub.2 (g)            -588    6 × 79                                                                        -163                                                                               2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1 kJ mol.sup.-1        -532    6 × 62                                                                        -175                                                                               2 × 42,                                                                        ΔG.sub.r.sup.0 (298 K.) = +69 kJ                                         mol.sup.-1,                                             [II-557]                                                                           MoO.sub.2 (cr) + 7 F(g) → MoF.sub.3 (g) + 2 OF.sub.2 (g)            -588    7 × 79                                                                        -607                                                                               2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -524 kJ                                        mol.sup.-1                                              -532    7 × 62                                                                        -596                                                                               2 × 42,                                                                        ΔG.sub.r.sup.0 (298 K.) = -414 kJ                                        mol.sup.-1,                                             [II-558]                                                                           MoO.sub.3 (cr) + 8 F(g) → MoF.sub.2 (g) + 3 OF.sub.2 (g)            -745    8 × 79                                                                        -163                                                                               3 × 24,                                                                        ΔH.sub. r.sup.0 (298 K.) = +22 kJ                                        mol.sup.-1                                              -668    8 × 62                                                                        -15 3 × 42,                                                                        ΔG.sub.r.sup.0 (298 K.) = +123 kJ                                        mol.sup.-1,                                             [II-559]                                                                           MoO.sub.3 (cr) + 9 F(g) → MoF.sub.3 (g) + 3 OF.sub.2 (g)            -745    9 × 79                                                                        -607                                                                               3 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -501 kJ                                        mol.sup.-1                                              -668    9 × 62                                                                        -596                                                                               3 × 42,                                                                        ΔG.sub.r.sup.0 (298 K.) = -360 kJ                                        mol.sup.-1,                                             [II-560]                                                                           MoCl.sub.2 (cr) + 8 F(g) → MoF.sub.2 (g) + 2 ClF.sub.3 (g)          -282    8 × 79                                                                        -163                                                                               2 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -831 kJ                                        mol.sup.-1,                                             [II-561]                                                                           MoCl.sub.2 (cr) + 9 F(g) → MoF.sub.3 (g) + 2 ClF.sub.3 (g)           -282   9 × 79                                                                        -607                                                                               2 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1354 kJ                                       mol.sup.-1,                                             [II-562]                                                                           MoCl.sub.3 (cr) + 11 F(g) → MoF.sub.2 (g) + 3 ClF.sub.3 (g)         -387    11 × 79                                                                       -163                                                                               3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1122 kJ                                       mol.sup.-1                                              and                                                                            [II-563]                                                                           MoCl.sub.3 (cr) + 12 F(g) → MoF.sub.3 (g) + 3 ClF.sub.3 (g)         -387    12 × 79                                                                       -607                                                                               3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1645 kJ                                       mol.sup.-1.                                             __________________________________________________________________________

Thus, we find for all molybdenum species the trifluoride and higher fluorides will form. Except for the reactions with the oxides the difluoride will also form.

    __________________________________________________________________________     [II-564]                                                                           Mo(cr) + 6 CO(g) → Mo(CO).sub.6 (cr)                                0       6 × -110                                                                       -983, ΔH.sub.r.sup.0 (298 K.) = -323 kJ mol.sup.-1         0       6 × -137                                                                       -878, ΔG.sub.r.sup.0 (298 K.) = -56 kJ mol.sup.-1,         [II-565]                                                                           MoO.sub.2 (cr) + 8 CO(g) → Mo(CO).sub.6 (cr) + 2 CO.sub.2 (g)       -588    8 × -110                                                                       -983                                                                               2 × -394, ΔH.sub.r.sup.0 (298 K.) = -303 kJ                        mol.sup.-1,                                                  -532    8 × -137                                                                       -878                                                                               2 × -394, ΔG.sub.r.sup.0 (298 K.) = -38 kJ                         mol.sup.-1,                                                  [II-566]                                                                           MoO.sub.3 (cr) + 9 CO(g) → Mo(CO).sub.6 (cr) + 3 CO.sub.2 (g)       -745    9 × -110                                                                       -983                                                                               3 × -394, ΔH.sub.r.sup.0 (298 K.) =  -430                          kJ mol.sup.-1                                                -668    9 × -137                                                                       -878                                                                               3 × -394, ΔG.sub.r.sup.0 (298 K.) = -159 kJ                        mol.sup.-1,                                                  [II-567]                                                                           MoCl.sub.2 (cr) + 8 CO(g) → Mo(CO).sub.6 (cr) + 2 COCl(g)           -282    8 × -110                                                                       -983                                                                                2 × -63, ΔH.sub.r.sup.0 (298 K.) = +53 kJ                         mol.sup.-1,                                                  [II-568]                                                                           MoCl.sub.2 (cr) + 8 CO*(g) → Mo(CO).sub.6 (cr) + 2 COCl(g)          -282    8 × 564                                                                        -983                                                                                2 × -63, ΔH.sub.r *(298 K.) = -5339 kJ                            mol.sup.-1,                                                  [II-569]                                                                           MoCl.sub.3 (cr) + 9 CO(g) → Mo(CO).sub.6 (cr) + 3 COCl(g)           -387    9 × -110                                                                       -983                                                                                3 × -63, ΔH.sub.r.sup.0 (298 K.) = +205 kJ                        mol.sup.-1                                                   and                                                                            [II-570]                                                                           MoCl.sub.3 (cr) + 9 CO*(g) → Mo(CO).sub.6 (cr) + 3 COCl(g)          -387    9 × 564                                                                        -983                                                                                3 × -63, ΔH.sub.r.sup.0 (298 K.) = -5861                          kJ mol.sup.-1.                                               __________________________________________________________________________

Thus, we have the choice of four procedures for the volatilization of molybdenum species:

O+F

O+CO

CO*.

4. TUNGSTEN

    ______________________________________                                         [II-571]                                                                             W(cr) + O(g) → WO(cr)                                             0         249     -272, ΔH.sub.r.sup.0 (298 K.) = -521 kJ                                  mol.sup.-1,                                                  [II-572]                                                                             WO(cr) + O(g) → WO.sub.2 (cr)                                     -272      249     -590, ΔH.sub.r.sup.0 (298 K.) = -567 kJ                                  mol.sup.-1                                                   and                                                                            [II-573]                                                                             WO.sub.2 (cr) + O(g) → WO.sub.3 (cr)                              -590      249     -842, ΔH.sub.r.sup.0 (298 K.) = -501 kJ                                  mol.sup.-1                                                   -534      232     -764, ΔG.sub.r.sup.0 (298 K.) = -462 kJ                                  mol.sup.-1.                                                  ______________________________________                                    

The trioxide probably will form as the liquid and then solidify.

The tetra-, penta- and hexachlorides all meet the criterion of [II-2] and will volatilize spontaneously in the Apparatus.

    ______________________________________                                         [II-574]                                                                             WCl.sub.2 (cr) + 7 O(g) → WO.sub.3 (cr) + 2 ClO.sub.2 (g)         -257       7 × 249                                                                           -842    2 × 102, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -2124 kJ mol.sup.-1                                -220       7 × 232                                                                           -764    2 × 120, ΔG.sub.r.sup.0 (298 K.)                                   =                                                                              -1928 kJ mol.sup.-1                                and                                                                            [II-575]                                                                             WCl.sub.3 (cr) + 9 O(g) → WO.sub.3 (cr) + 3 ClO.sub.2 (g)         -357       9 × 249                                                                           -842    3 × 102, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -2420 kJ mol.sup.-1.                               ______________________________________                                    

The enthalpy of sublimation of the trioxide is 549 kJ mol⁻¹ with a `times four` factor of 2196 kJ mol⁻¹. Thus, the trioxide formed in [II-565] will volatilize. Since the monoxygen is at least in part in an excited state, the same comment applies to [II-574].

The `times four` criterion for the volatilization of the di- and tri-fluorides are 1680 and 1260 kJ mol⁻¹, respectively.

    ______________________________________                                         [II-576] W(cr) + 2 F(g) → WF.sub.2 (cr)                                        0      2 × 79                                                                            -608, ΔH.sub.r.sup.0 (298 K.) =                                          -766 kJ mol.sup.-1,                                     [II-577] WF.sub.2 (cr) + F(g) → WF.sub.3 (cr)                                  -608   79       -923, ΔG.sub.r.sup.0 (298 K.) =                                          -394 kJ mol.sup.-1                                      and                                                                            [II-578] WF.sub.3 (cr) + F(g) → WF.sub.4 (cr)                                  -923   79       -1208, ΔH.sub.r.sup.0 (298 K.) =                                         -364 kJ mol.sup.-1.                                     ______________________________________                                    

Since 766+394+364=1524 and since the `times four` criterion for the tetrafluoride is 712 kJ mol⁻¹, the tetrafluoride will volatilize. Higher fluorides may also be formed. They a fortiori will volatilize.

    __________________________________________________________________________     [II-579]                                                                           WO(cr) + 6 F(g) → WF.sub.4 (cr) + OF.sub.2 (g)                      -272    6 × 79                                                                         -1208                                                                              24,   ΔH.sub.r.sup.0 (298 K.) = -1386 kJ                                       mol.sup.-1,                                            [II-580]                                                                           WO.sub.2 (cr) + 8 F(g) → WF.sub.4 (cr) + 2 OF.sub.2 (g)             -590    8 × 79                                                                         -1208                                                                              2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1202 kJ                                       mol.sup.-1,                                            [II-581]                                                                           WO.sub.3 (cr) + 10 F(g) → WF.sub.4 (cr) + 3 OF.sub.2 (g)            -842    10 × 79                                                                        -1208                                                                              3 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1084 kJ                                       mol.sup.-1,                                            [II-582]                                                                           WCl.sub.2 (cr) + 10 F(g) → WF.sub.4 (cr) + 2 ClF.sub.3 (g)          -257    10 × 79                                                                        -1208                                                                              2 ×  -159,                                                                     ΔH.sub.r.sup.0 (298 K.) = -2059 kJ                                       mol.sup.-1                                             and                                                                            [II-583]                                                                           WCl.sub.3 (cr) + 13 F(g) → WF.sub.4 (cr) + 3 ClF.sub.3 (g)          -357    13 × 79                                                                        -1208                                                                              3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2355 kJ                                       mol.sup.-1.                                            [II-584]                                                                           W(cr) + 6 CO(g) → W(CO).sub.6 (cr)                                  0       6 × -111                                                                       -960, ΔH.sub.r.sup.0 (298 K.) = -294 kJ mol.sup.-1,        [II-585]                                                                           W(cr) + 6 CO*(g) → W(CO).sub.6 (cr)                                 0       6 × 564                                                                        -960, ΔH.sub.r *(298 K.) = -4344 kJ mol.sup.-1,            [II-586]                                                                           WO(cr) + 7 CO(g) → W(CO).sub.6 (cr) + CO.sub.2 (g)                  -272    7 × -111                                                                       -960                                                                               -394, ΔH.sub.r.sup.0 (298 K.) =  -305 kJ                                       mol.sup.-1,                                            [II-587]                                                                           WO.sub.2 (cr) + 8 CO(g) → W(CO).sub.6 (cr) + 2 CO.sub.2 (g)         -590    8 × -111                                                                       -960                                                                               2 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -270 kJ                                        mol.sup.-1,                                            [II-588]                                                                           WO.sub.2 (cr) + 8 CO*(g) → W(CO).sub.6 (cr) + CO.sub.2 (g)          -590    8 × 564                                                                        -960                                                                               2 × -394,                                                                      ΔH.sub.r *(298 K.) = -5670 kJ mol.sup.-1,        [II-589]                                                                           WO.sub.3 (cr) + 9 CO(g) → W(CO).sub.6 (cr) + 3 CO.sub.2 (g)         -842    9 × -111                                                                       -960                                                                               3 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -301 kJ                                        mol.sup.-1,                                            [II-590]                                                                           WO.sub.3 (cr) + 9 CO*(g) → W(CO).sub.6 (cr) + 3 CO.sub.2 (g)        - 842   9 × 564                                                                        -960                                                                               3 × -394,                                                                      ΔH.sub.r *(298 K.) = -6376 kJ mol.sup.-1,        [II-591]                                                                           WCl.sub.2 (cr) + 8 CO(g) → W(CO).sub.6 (cr) + 2 COCl(g)             -257    8 × -111                                                                       -960                                                                               2 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +59 kJ                                         mol.sup.-1,                                            [II-592]                                                                           WCl.sub.2 (cr) + 8 CO*(g) → W(CO).sub.6 (cr) + 2 COCl(g)            -257    8 × 564                                                                        -960                                                                               2 × -63,                                                                       ΔH.sub.r *(298 K.) = -5341 kJ mol.sup.-1,        [II-593]                                                                           WCl.sub.3 (cr) + 9 CO(g) → W(CO).sub.6 (cr) + 3 COCl(g)             -357    9 × -111                                                                       -960                                                                               3 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +207 kJ                                        mol.sup.-1,                                            [II-594]                                                                           WCl.sub.3 (cr) + 9 CO*(g) → W(CO).sub.6 (cr) + 3 COCl(g)            -357    9 × 564                                                                        -960                                                                               3 × -63,                                                                       ΔH.sub.r *(298 K.) = -5868 kJ mol.sup.-1,        [II-595]                                                                           WF.sub.2 (cr) + 8 CO(g) → W(CO).sub.6 (cr) + 2 COF(g)               -602    8 × -111                                                                       -960                                                                               2 × -172,                                                                      ΔH.sub.r.sup.0 (298 K.) = +186 kJ                                        mol.sup.-1,                                            [II-596]                                                                           WF.sub.2 (cr) + 8 CO*(g) → W(CO).sub.6 (cr) + 2 COF(g)              -602    8 × 564                                                                        -960                                                                               2 × -172,                                                                      ΔH.sub.r *(298 K.) = -5214 kJ mol.sup.-1,        [II-597]                                                                           WF.sub.3 (cr) + 9 CO(g) → W(CO).sub.6 (cr) + 3 COF(g)               -923    9 × -111                                                                       -960                                                                               3 × -172,                                                                      ΔH.sub.r.sup.0 (298 K.) = +446 kJ                                        mol.sup.-1,                                            [II-598]                                                                           WF.sub.3 (cr) + 9 CO*(g) → W(CO).sub.6 (cr) + 3 COF(g)              -923    9 × 564                                                                        -960                                                                               3 × -172,                                                                      ΔH.sub.r *(298 K.) = -5629 kJ mol.sup.-1,        [II-599]                                                                           WF.sub.4 (cr) + 10 CO(g) → W(CO).sub.6 (cr) + 4 COF(g)              -1208   10 × -111                                                                      -960                                                                               4 × -172,                                                                      ΔH.sub.r.sup.0 (298 K.) = +670 kJ                                        mol.sup.-1,                                            [II-600]                                                                           WF.sub.4 (cr) + 10 CO*(g) → W(CO).sub.6 (cr) + 4 COF(g)             -1208   10 × 564                                                                       -960                                                                               4 × -172,                                                                      ΔH.sub.r *(298 K.) = -6080 kJ mol.sup.-1,        [II-601]                                                                           WF.sub.5 (cr) + 11 CO(g) → W(CO).sub.6 (cr) + 5 COF(g)              -1495   11 × -111                                                                      -960                                                                               5 × -172,                                                                      ΔH.sub.r.sup.0 (298 K.) = +896 kJ                                        mol.sup.-1,                                            and                                                                            [II-602]                                                                           WF.sub.5 (cr) + 11 CO*(g) → W(CO).sub.6 (cr) + 5 COF(g)             -1495   11 × 564                                                                       -960                                                                               5 × -172,                                                                      ΔH.sub.r *(298 K.) = -6529 kJ mol.sup.-1.        [II-603]                                                                           W(cr) + 6 CH.sub.3 (g) → (CH.sub.3).sub.6 W(l)                      0       6 × 146                                                                        739, ΔH.sub.r.sup.0 (298 K.) = -137 kJ mol.sup.-1,         [II-604]                                                                           WO(cr) + 8 CH.sub.3 (g) → (CH.sub.3).sub.6 W(l)                         + (CH.sub.3).sub.2 O(g)                                                    -272    8 × 146                                                                        739 -184, ΔH.sub.r.sup.0 (298 K.) = -341 kJ                                        mol.sup.-1,                                            [II-605]                                                                           WO.sub.2 (cr) + 10 CH.sub.3 (g) → (CH.sub.3).sub.6 W(l) + 2             (CH.sub.3).sub.2 (g)                                                       -590    10 × 146                                                                       739 2 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -499 kJ                                        mol.sup.-1,                                            [II-606]                                                                           WO.sub.3 (cr) + 12 CH.sub.3 (g) → (CH.sub.3).sub.6 W(l) + 3             (CH.sub.3).sub.2 O(g)                                                      -842    12 × 146                                                                       739 3 × -184,                                                                      ΔH.sub.r.sup.0 (298 K.) = -723 kJ                                        mol.sup.-1,                                            [II-607]                                                                           WCl.sub.2 (cr) + 8 CH.sub.3 (g) → (CH.sub.3).sub.6 W(l) + 2             CH.sub.3 Cl(g)                                                             -257    8 × 146                                                                        739 2 × -84,                                                                       ΔH.sub.r.sup.0 (298 K.) = -340 kJ                                        mol.sup.-1,                                            [II-608]                                                                           WCl.sub.3 (cr) + 9 CH.sub.3 (g) → (CH.sub.3)6W(l) + 3 CH.sub.3          Cl(g)                                                                      -357    9 × 146                                                                        739 3 ×  -84,                                                                      ΔH.sub.r.sup.0 (298 K.) = -470 kJ                                        mol.sup.-1,                                            [II-609]                                                                           WF.sub.2 (cr) + 8 CH.sub.3 (g) → (CH.sub.3)6W(l) + 2 CH.sub.3           F(g)                                                                       -602    8 × 146                                                                        739 2 × -234,                                                                      ΔH.sub.r.sup.0 (298 K.) = -295 kJ                                        mol.sup.-1,                                            [II-610]                                                                           WF.sub.3 (cr) + 9 CH.sub.3 (g) → (CH.sub.3).sub.6 W(l) + 3              CH.sub.3 F(g)                                                              -923    9 × 146                                                                        739 3 × -234,                                                                      ΔH.sub.r.sup.0 (298 K.) = -354 kJ                                        mol.sup.-1,                                            [II-611]                                                                           WF.sub.4 (cr) + 10 CH.sub.3 (g) → (CH.sub.3).sub.6 W(l) + 4             CH.sub.3 F(g)                                                              -1208   10 × 146                                                                       739 4 × -234,                                                                      ΔH.sub.r.sup.0 (298 K.) = -449 kJ                                        mol.sup.-1,                                            and                                                                            [II-612]                                                                           WF.sub.5 (cr) + 11 CH.sub.3 (g) → (CH.sub.3).sub.6 W(l) + 5             CH.sub.3 F(g)                                                              -1495   11 × 146                                                                       739 5 × -234,                                                                      ΔH.sub.r.sup.0 (298 K.) = -542 kJ                                        mol.sup.-1.                                            __________________________________________________________________________

Thus, we have the choice of five procedures for the volatilization of tungsten species:

O+F

O+CO*

O+CH₃

CH₃.

N. Group VII B.

1. [II-THERMODYNAMICS

The `times four` criterion for the species of interest at

    ______________________________________                                         MnF.sub.2                                                                               1044 kJ mol.sup.-1                                                                          ReF.sub.3  640 kJ mol.sup.-1                             MnF.sub.3                                                                                888         ReF.sub.4  528                                           Mn.sub.2 (CO).sub.10                                                                     252         ReF.sub.5  328                                                                 ReF.sub.6  116                                           Re.sub.2 O.sub.7                                                                         552         Re.sub.2 (CO).sub.10                                                                      372.                                          ______________________________________                                    

                  TABLE II-17                                                      ______________________________________                                         GROUP VII B.                                                                   THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kj mol.sup.-1)                                                                SPECIES       Mn           Re                                                  ______________________________________                                         MO        (cr)    -385a/-363a                                                            (g)     +124a/--                                                     M.sub.3 O.sub.4                                                                          (cr)    -1388a/-1283a                                                M.sub.2 O.sub.3                                                                          (cr)     -959a/-881a-                                                MO.sub.2  (cr)    -520a/-465a                                                  MO.sub.3  (cr)                 -611b/-531b                                     M.sub.2 O.sub.7                                                                          (cr)                 -1238b/-1084b                                             (g)                  -1100a/-994a                                    MCl       (g)     +42a/--                                                                (g)     -264a/--                                                     MF        (g)     -22a/--                                                      MF.sub.2  (cr)    -795c/--                                                               (g)     -534c/--                                                     MF.sub.3  (cr)    -996c/--     -711c/--                                                  (g)     -774c/--     -551c/                                          MF.sub.4  (cr)                 -920c/--                                                  (g)                  -788c/--                                        MF.sub.5  (cr)                 -941c/--                                                  (g)                  -859c/--                                        MF.sub.6  (l)                  -1151b/-1054b                                             (g)                  -1122c/--                                       MCL.sub.3 (cr)                 -264b/-201b                                     MCL.sub.5 (cr)                 -372a/--                                                  (g)     -318a/--                                                     M.sub.2 (CO).sub.10                                                                      (cr)    -1678a/--    -1651d/--                                                 (g)     -1615a/--    -1558d/--                                       ______________________________________                                          (a. Ref. <B>, b. Ref. <II28>, c. Ref. <II23>, d. Ref. <II15>).           

2. MANGANESE

    __________________________________________________________________________     [II-613]                                                                            Mn(cr) + O(g) → MnO(cr)                                            0          249   -385,  ΔH.sub.r.sup.0 (298 K.) = -634 kJ                                        mol.sup.-1                                             0          203,  -363,  ΔG.sub.r.sup.0 (298 K.) = -566 kJ                                        mol.sup.-1,                                            [II-614]                                                                            MnO(cr) + 1/3 O(g) → 1/3 Mn.sub.3 O.sub.4 (cr)                     -385       1/3 × 249                                                                      1/3 × -1388,                                                                    ΔH.sub.r.sup.0 (298 K.) = -161 kJ                                        mol.sup.-1                                             -363       1/3 × 203                                                                      1/3 × -1283,                                                                    ΔG.sub.r.sup.0 (298 K.) = -132 kJ                                        mol.sup.-1,                                            [II-615]                                                                            1/3 Mn.sub.3 O.sub.4 (cr) + 1/6 O(g) → 1/2 Mn.sub.2 O.sub.3             (cr)                                                                      1/3 × -1388                                                                         1/6 × 249                                                                      1/2 × -959,                                                                     ΔH.sub.r.sup.0 (298 K.) = -58 kJ                                         mol.sup.-1                                             1/3 × -1283                                                                         1/6 × 203                                                                      1/2 × -881,                                                                     ΔG.sub.r.sup.0 (298 K.) = -47 kJ                                         mol.sup.-1,                                            [II-616]                                                                            1/2 Mn.sub.2 O.sub.3 (cr) + 1/2 O(g) → MnO.sub.2 (cr)              1/2 × -959                                                                          1/2 × 249                                                                      -520,  ΔH.sub.r.sup.0 (298 K.) = -165 kJ                                        mol.sup.-1                                             1/2 × -881                                                                          1/2 × 203                                                                      -465,  ΔG.sub.r.sup.0 (298 K.) = -126 kJ                                        mol.sup.-1,                                            [II-617]                                                                            MnCl.sub.2 (cr) + 5 O(g) → MnO(cr) + 2 ClO.sub.2 (g)               -481       5 × 249                                                                        -385                                                                               2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -945 kJ                                        mol.sup.-1                                           -440       5 × 232                                                                        -363                                                                               2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -843 kJ                                        mol.sup.-1,                                          [II-618]                                                                            MnF.sub.2 (cr) + 5 O(g) → MnO(cr) + 2 FO.sub.2 (g)                 -795       5 × 249                                                                        -385                                                                               2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -809 kJ                                        mol.sup.-1                                           and                                                                            [II-619]                                                                            MnF.sub.3 (cr) + 7 O(g) → MnO(cr) + 3 FO.sub.2 (g)                 -996       7 × 249                                                                        -385                                                                               3 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1093 kJ                                       mol.sup.-1.                                          [II-620]                                                                            Mn(cr) + 2 F(g) → MnF.sub.2 (cr)                                   0          2 × 79                                                                         -795, ΔH.sub.r.sup.0 (298 K.) = -953 kJ                                        mol.sup.-1,                                             [II-621]                                                                            Mn(cr) + 3 F(g) → MnF.sub.3 (cr)                                   0          3 × 79                                                                         -996, ΔH.sub.r.sup.0 (298 K.) = -1233 kJ                                       mol.sup.-1,                                             [II-622]                                                                            MnO(cr) + 4 F(g) → MnF.sub.2 (cr) + OF.sub.2 (g)                   -385       4 ×  79                                                                        -795                                                                               13,  ΔH.sub.r.sup.0 (298 K.) = -713 kJ                                        mol.sup.-1,                                          [II-623]                                                                            MnO(cr) + 5 F(g) → MnF.sub.3 (cr) + OF.sub.2 (g)                   -385       5 × 79                                                                         -996                                                                               13,  ΔH.sub.r.sup.0 (298 K.) = -993 kJ                                        mol.sup.-1,                                          [II-624]                                                                            1/3 Mn.sub.3 O.sub.r (cr) + 14/3 F(g) → MnF.sub.2 (cr) + 4/3            OF.sub.2 (g)                                                              1/3 × -1388                                                                         14/3 × 79                                                                      -795                                                                               4/3 × 13,                                                                     ΔH.sub.r.sup.0 (298 K.) = -684 kJ                                        mol.sup.-1,                                          [II-624a]                                                                           1/3 Mn.sub.3 O.sub.4 (cr) + 17/3 F(g) → MnF.sub.3 (cr) + 4/3            OF.sub.2 (g)                                                              1/3 × -1388                                                                         17/3 × 79                                                                      -996                                                                               4/3 × 13,                                                                     ΔH.sub.r.sup.0 (298 K.) = -964 kJ                                        mol.sup.-1,                                          [ II-625]                                                                           1/2 Mn.sub.2 O.sub.3 (cr) + 5 F(g) → MnF.sub.2 (cr) + 3/2               OF.sub.2 (g)                                                              0.5 × -959                                                                          5 × 79                                                                         -795                                                                               1.5 × 13,                                                                     ΔH.sub.r.sup.0 (298 K.) = -691 kJ                                        mol.sup.-1,                                          [II-626]                                                                            1/2 Mn.sub.2 O.sub.3 (cr) + 6 F(g) → MnF.sub.3 (cr) + 3/2               OF.sub.2 (g)                                                              0.5 × -959                                                                          6 × 79                                                                         -996                                                                               1.5 × 13,                                                                     ΔH.sub.r.sup.0 (298 K.) = -971 kJ                                        mol.sup.-1,                                          [II-627]                                                                            MnO.sub.2 (cr) + 6 F(g) → MnF.sub.2 (cr) + 2 OF.sub.2 (g)          -520       6 × 79                                                                         -795                                                                               2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -723 kJ                                        mol.sup.-1,                                          [II-628]                                                                            MnO.sub.2 (cr) + 7 F(g) → MnF.sub.3 (cr) + 2 OF.sub.2 (g)          -520       7 × 79                                                                         -996                                                                               2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1003 kJ                                       mol.sup.-1,                                          [II-629]                                                                            MnCl.sub.2 (cr) + 8 F(g) → MnF.sub.2 (cr) + 2 ClF.sub.3 (g)        -481       8 × 79                                                                         -795                                                                               2 × -159,                                                                     ΔH.sub.r.sup.0 (298 K.) = -1264 kJ                                       mol.sup.-1                                           and                                                                            [II-630]                                                                            MnCl.sub.2 (cr) + 9 F(g) → MnF.sub.3 (cr) + 2 ClF.sub.3 (g)        -481       9 × 79                                                                         -996                                                                               2 × -159,                                                                     ΔH.sub.r.sup.0 (298 K.) = -1544 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

Thus, ground state monofluorine is an effective volatilizing reagent for all the manganese species except for the fluorides. Unless one is certain that there are no fluoride species present, the safe procedure is O+F.

    __________________________________________________________________________     [II-631]                                                                           2 Mn(cr) + 10 CO(g) → Mn.sub.2 (CO).sub.10 (cr)                     0     10 × -111                                                                      -1678, ΔH.sub.r.sup.0 (298 K.) = -568 kJ mol.sup.-1          [II-632]                                                                           2 MnO(cr) + 12 CO(g) → Mn.sub.2 (CO).sub.10 (cr) + 2 CO.sub.2           (g)                                                                        2 × -385                                                                           12 × -111                                                                       -1678                                                                              2 × -394,                                                                       ΔH.sub.r.sup.0 298 K.) = -364 kJ                                         mol.sup.-1,                                        [II-633]                                                                           2/3Mn.sub.3 O.sub.4 (cr) + 38/3 CO(g) → Mn.sub.2 (CO).sub.10            (cr) + 8/3 CO.sub.2 (g)                                                    2/3 × -1388                                                                        38/3 × -111                                                                     -1678                                                                              8/3 × -394,                                                                     ΔH.sub.r.sup.0 (298 K.) = -397 kJ                                        mol.sup.-1,                                        [II-634]                                                                           Mn.sub.2 O.sub.3 (cr) + 13 CO(g) → Mn.sub.2 (CO).sub.10 (cr) +          3 CO.sub.2 (g)                                                             -959      13 × -111                                                                       -1678                                                                              3 × -394,                                                                       ΔH.sub.r.sup.0 (298 K.) = -458 kJ                                        mol.sup.-1,                                        [II-635]                                                                           2 MnO.sub.2 (cr) + 14 CO(g) → Mn.sub.2 (CO).sub.10 (cr) + 4             CO.sub.2 (g)                                                               2 × 520                                                                            14 × -111                                                                       -1678                                                                              4 × -394,                                                                       ΔH.sub.r.sup.0 (298 K.) = -660 kJ                                        mol.sup.-1,                                        [II-636]                                                                           2 MnCl.sub.2 (cr) + 14 CO(g) → Mn.sub.2 (CO).sub.10 (cr) + 4            COCl(g)                                                                    2 × -481                                                                           14 × -111                                                                       -1678                                                                              4 × -63,                                                                        ΔH.sub.r.sup.0 (298 K.) = +586 kJ                                        mol.sup.-1,                                        [II-637]                                                                           2 MnCl.sub.2 (cr) + 14 CO*(g) → Mn.sub.2 (CO).sub.10 (cr) + 4           COCl(g)                                                                    2 × -481                                                                           14 × 564                                                                        -1678                                                                              4 × - 63,                                                                       ΔH.sub.r *(298 K.) = -8864 kJ                                            mol.sup.-1,                                        [II-638]                                                                           2 MnF.sub.2 (cr) + 14 CO(g) → Mn.sub.2 (CO).sub.10 (cr) + 4             COF(g)                                                                     2 × -795                                                                           14 × -111                                                                       -1678                                                                              4 × -172,                                                                       ΔH.sub.r.sup.0 (298 K.) = +778 kJ                                        mol.sup.-1,                                        [II-639]                                                                           2 MnF.sub.2 (cr) + 14 CO*(g) → Mn.sub.2 (CO).sub.10 (cr) + 4            COF(g)                                                                     2 × -795                                                                           14 × 564                                                                        -1678                                                                              4 × -172,                                                                       ΔH.sub.r *(298 K.) = -8672 kJ                                            mol.sup.-1,                                        [II-640]                                                                           2 MnF.sub.3 (cr) + 16 CO(g) → Mn.sub.2 (CO).sub.10 (cr) + 6             COF(g)                                                                     2 × -996                                                                           16 × -111                                                                       -1678                                                                              6 × -172,                                                                       ΔH.sub.r.sup.0 (298 K.) = +1058 kJ                                       mol.sup.-1                                         and                                                                            [II-641]                                                                           2 MnF.sub.3 (cr) + 16 CO*(g) → Mn.sub.2 (CO).sub.10 (cr) + 6            COF(g)                                                                     2 × -996                                                                           16 × 564                                                                        -1678                                                                              6 × -172,                                                                       ΔH.sub.r *(298 K.) = -9742 kJ                                            mol.sup.-1.                                        __________________________________________________________________________

Thus, we have the choice of three procedures for the volatilization of manganese species:

O+F

O+CO

CO*.

3. RHENIUM

    ______________________________________                                         [II-642]                                                                             Re(cr) + 2 O(g) → ReO.sub.2 (cr)                                  0            2 × 249                                                                             -423, ΔH.sub.r.sup.0 (298 K.) =                                          -921 kJ mol.sup.-1                                     0            2 × 232                                                                             -372, ΔG.sub.r.sup.0 (298 K.) =                                          -836 kJ mol.sup.-1,                                    [II-643]                                                                             ReO.sub.2 (cr) + O(g) → ReO.sub.3 (cr)                            -423         249        -611, ΔH.sub.r.sup.0 (298 K.) =                                          -437 kJ mol.sup.-1                                     -372         232        -531, ΔH.sub.r.sup.0 (298 K.) =                                          -391 kJ mol.sup.-1,                                    [II-644]                                                                             2 Re(cr) + 7 O(g) → Re.sub.2 O.sub.7 (cr)                         0            7 × 249                                                                             -1238, ΔH.sub.r.sup.0 (298 K.) =                                         -2981 kJ mol.sup.-1                                    0            7 × 232                                                                             -1084, ΔG.sub.r.sup.0 (298 K.) =                                         -2708 kJ mol.sup.-1,                                   [ II-645]                                                                            2 ReO.sub.2 (cr) + 3 O(g) → Re.sub.2 O.sub.7 (cr)                 2 × -423                                                                              3 × 249                                                                             -1238, ΔH.sub.r.sup.0 (298 K.) =                                         -1139 kJ mol.sup.-1                                    2 × -372                                                                              3 × 232                                                                             -1084, ΔG.sub.r.sup.0 (298 K.) =                                         -1036 kJ mol.sup.-1,                                   [II-646]                                                                             2 ReO.sub.3 (cr) + O(g) → Re.sub.2 O.sub.7 (cr)                   2 × -611                                                                              249        -1238, ΔH.sub.r.sup.0 (298 K.) =                                         -265 kJ mol.sup.-1                                     2 × -531                                                                              232        -1084, ΔG.sub.r.sup.0 (298 K.) =                                         -254 kJ mol.sup.-1                                     and                                                                            [II-647]                                                                             2 ReO.sub.3 (cr) + O*(g) → Re.sub.2 O.sub.7 (cr)                  2 × -611                                                                              529        -1238, ΔH.sub.r *(298 K.) =                                              -545 kJ mol.sup.-1.                                    ______________________________________                                    

Since the `times four` criterion for Re₂ O₇ is 552 kJ mol⁻¹, even excited state monoxygen cannot be expected to be effective in the volatilization of the trioxide.

    __________________________________________________________________________     [II-648]                                                                           2 ReCl.sub.3 (cr) + 19 O(g) → Re.sub.2 O.sub.7 (cr) + 6                 ClO.sub.2 (g)                                                              2 × -264                                                                           19 × 249                                                                      -1238                                                                              6 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -4829 kJ                                       mol.sup.-1                                             2 × -201                                                                           19 × 232                                                                      -1084                                                                              6 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -4370 kJ                                       mol.sup.-1,                                            [II-649]                                                                           2 ReCl.sub.5 (cr) + 27 O(g) → Re.sub.2 O.sub.7 (cr) + 10                ClO.sub.2 (g)                                                              2 × -372                                                                           27 × 249                                                                      -1238                                                                              10 × 102,                                                                     ΔH.sub.r.sup.0 (298 K.) = -6197 kJ                                       mol.sup.-1,                                            [II-650]                                                                           2 ReF.sub.3 (cr) + 19 O(g) → Re.sub.2 O.sub.7 (cr) + 6                  FO.sub.2 (g)                                                               2 × -711                                                                           19 × 249                                                                      -1238                                                                              6 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -4469 kJ                                       mol.sup.-1,                                            [II-651]                                                                           2 ReF.sub.4 (cr) + 23 O(g) → Re.sub.2 O.sub.7 cr) + 8 FO.sub.2          (g)                                                                        2 × -920                                                                           23 × 249                                                                      -1238                                                                              8 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -5021 kJ                                       mol.sup.-1,                                            [II-652]                                                                           2 ReF.sub.5 (cr) + 27 O(g) → Re.sub.2 O.sub.7 (cr) + 10                 FO.sub.2 (g)                                                               2 × -941                                                                           27 × 249                                                                      -1238                                                                              10 × 13,                                                                      ΔH.sub.r.sup.0 (298 K.) = -5949 kJ                                       mol.sup.-1                                             and                                                                            [II-653]                                                                           2 ReF.sub.6 (cr) + 31 O(g) → Re.sub.2 O.sub.7 (cr) + 12                 FO.sub.2 (g)                                                               2 × -1151                                                                          31 × 249                                                                      -1238                                                                              12 × 13,                                                                      ΔH.sub.r.sup.0 (298 K.) = -6499 kJ                                       mol.sup.-1                                             2 × -1054                                                                          31 × 232                                                                      -1084                                                                              12 × 27, ΔG.sub.r.sup.0 (298 K.) = -5844                           kJ mol.sup.-1.                                              __________________________________________________________________________

Thus, we find that even ground state monoxygen is effective in the volatilization of the halides.

    __________________________________________________________________________     [II-654]                                                                           Re(cr) + 3 F(g) → ReF.sub.3 (cr)                                    0       3 × 79                                                                       -711,                                                                              ΔH.sub.r.sup.0 (298 K.) = -948 kJ mol.sup.-1,            [II-655]                                                                           ReF.sub.3 (cr) + F(g) → ReF.sub.4 (cr)                              -711    79  -920,                                                                              ΔH.sub.r.sup.0 (298 K.) = -288 kJ mol.sup.-1,            [II-656]                                                                           ReF.sub.4 (cr) + F(g) → ReF.sub.5 (cr)                              -920    79  -941,                                                                              ΔH.sub.r.sup.0 (298 K.) = -100 kJ mol.sup.-1,            [II-657]                                                                           ReF.sub.3 (cr) + 3 F(g) → ReF.sub.6 (cr)                            -711    3 × 79                                                                       -1151,                                                                             ΔH.sub.r.sup.0 (298 K.) = -677 kJ mol.sup.-1,            [II-658]                                                                           ReF.sub.4 (cr) + 2 F(g) → ReF.sub.6 (cr)                            -920    2 × 79                                                                       -1151,                                                                             ΔH.sub.r.sup. 0 (298 K.) = -389 kJ mol.sup.-1            and                                                                            [II-659]                                                                           ReF.sub.5 (cr) + F(g) → ReF.sub.6 (cr)                              -941    79  -1151,                                                                             ΔH.sub.r.sup.0 (298 K.) = -289 kJ mol.sup.-1.            [II-660]                                                                           ReO.sub.2 (cr) + 10 F(g) → ReF.sub.6 (cr) + 2 OF.sub.2 (g)          -423      10 × 79                                                                       -1151                                                                              2 × 24,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1470 kJ                                       mol.sup.-1                                           -372      10 × 62                                                                       -1122                                                                              2 × 42,                                                                         ΔG.sub.r.sup.0 (298 K.) = -1286 kJ                                       mol.sup.-1,                                          [II-661]                                                                           ReO.sub.3 (cr) + 12 F(g) → ReF.sub.6 (cr) + 3 OF.sub.2 (g)          -611      12 × 79                                                                       -1151                                                                              3 × 24,                                                                         ΔH.sub.r.sup.0 (298 K.) = -1416 kJ                                       mol.sup.-1                                           -531      12 × 62                                                                       -1122                                                                              3 × 42,                                                                         ΔG.sub.r.sup.0 (298 K.) = -1209 kJ                                       mol.sup.-1,                                          [II-662]                                                                           0.5 Re.sub.2 O.sub.7 (cr) + 13 F(g) → ReF.sub.6 (cr) + 3.5              OF.sub.2 (g)                                                               0.5 × -1238                                                                        13 × 79                                                                       -1151                                                                              3.5 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1475 kJ                                       mol.sup.-1                                           0.5 × -1084                                                                        13 × 62                                                                       -1122                                                                              3.5 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1239 kJ                                       mol.sup.-1,                                          [II-663]                                                                           ReCl.sub.3 (cr) + 15 F(g) → ReF.sub.6 (cr) + 3 ClF.sub.3 (g)        -264      15 × 79                                                                       -1151                                                                              3 × -159,                                                                     ΔH.sub.r.sup.0 (298 K.) = -2549 kJ                                       mol.sup.-1                                             -201      15 × 62                                                                       -1122                                                                              3 × -119,                                                                     ΔG.sub.r.sup.0 (298 K.) = -2208 kJ                                       mol.sup.-1                                             and                                                                            [II-664]                                                                           ReCl.sub.5 (cr) + 21 F(g) → ReF.sub.6 (cr) + 5 ClF.sub.3 (g)        -372      21 × 79                                                                       -1151                                                                              5 × -159,                                                                     ΔH.sub.r.sup.0 (298 K.) = -3233 kJ                                       mol.sup.-1.                                            [II-665]                                                                           2 Re(cr) + 10 CO(g) → Re.sub.2 (CO).sub.10 (cr)                     0       10 × -110                                                                    -1651,      ΔH.sub.r.sup.0 (298 K.) = -551 kJ                                        mol.sup.-1,                                            [II-666]                                                                           2 ReO.sub.2 (cr) + 14 CO(g) → Re.sub.2 (CO).sub.10 (cr) + 4             CO.sub.2 (g)                                                               2 × -423                                                                           14 × -110                                                                     -1651                                                                              4 × -394,                                                                     ΔH.sub.r.sup.0 (298 K.) = -841 kJ                                        mol.sup.-1,                                            [II-667]                                                                           2 ReO.sub.3 (cr) + 16 CO(g) → Re.sub.2 (CO).sub.10 (cr) + 6             CO.sub.2 (g)                                                               2 × -611                                                                           16 × -110                                                                     -1651                                                                              6 × -394,                                                                     ΔH.sub.r.sup.0 (298 K.) = -1033 kJ                                       mol.sup.-1,                                            [II-668]                                                                           Re.sub.2 O.sub.7 (cr) + 17 CO(g) → Re.sub.2 (CO).sub.10 (cr) +          7 CO.sub.2 (g)                                                             -1238     17 × -110                                                                     -1651                                                                              7 × -394,                                                                     ΔH.sub.r.sup.0 (298 K.) = -1301 kJ                                       mol.sup.-1,                                            [II-669]                                                                           2 ReCl.sub.3 (cr) + 16 CO(g) → Re.sub.2 (CO).sub.10 (cr) + 6            COCl(g)                                                                    2 × -264                                                                           16 × -110                                                                     -1651                                                                              6 × -63,                                                                      ΔH.sub.r.sup.0 (298 K.) = +259 kJ                                        mol.sup.-1,                                            [II-670]                                                                           2 ReCl.sub.3 (cr) + 16 CO*(g) → Re.sub.2 (CO).sub.10 (cr) + 6           COCl(g)                                                                    2 × -264                                                                           16 × 564                                                                      -1651                                                                              6 × -63,                                                                      ΔH.sub.r *(298 K.) = -10,525 kJ                                          mol.sup.-1,                                            [II-671]                                                                           2 ReCl.sub.5 (cr) + 20 CO(g) → Re.sub.2 (CO).sub.10 (cr) + 10           COCl(g)                                                                    2 × -372                                                                           20 × -110                                                                     -1651                                                                              10 × -63,                                                                     ΔH.sub.r.sup.0 (298 K.) = +663 kJ                                        mol.sup.-1,                                            [II-672]                                                                           2 ReCl.sub.5 (cr) + 20 CO*(g) → Re.sub.2 (CO).sub.10 (cr) + 10          COCl(g)                                                                    2 × -372                                                                           20 × 564                                                                      -1651                                                                              10 × -63,                                                                     ΔH.sub.r *(298 K.) = -12,817 kJ                                          mol.sup.-1,                                            [II-673]                                                                           2 ReF.sub.3 (cr) + 16 CO(g) → Re.sub.2 (CO).sub.10 (cr) + 6             COF(g)                                                                     2 × -711                                                                           16 × -110                                                                     -1651                                                                              6 × -172,                                                                     ΔH.sub.r.sup.0 (298 K.) = +499 kJ                                        mol.sup.-1,                                            [II-674]                                                                           2 ReF.sub.3 (cr) + 16 CO*(g) → Re.sub.2 (CO).sub.10 (cr) +  6           COF(g)                                                                     2 × -711                                                                           16 × 564                                                                      -1651                                                                              6 × -172,                                                                     ΔH.sub.r *(298 K.) = -10,285 kJ                                          mol.sup.-1,                                            [II-675]                                                                           2 ReF.sub.4 (cr) + 18 CO(g) → Re.sub.2 (CO).sub.10 (cr) + 8             COF(g)                                                                     2 × -920                                                                           18 × -110                                                                     -1651                                                                              8 × -172,                                                                     ΔH.sub.r.sup.0 (298 K.) = +793 mol.sup.-1,       [II-676]                                                                           2 ReF.sub.4 (cr) + 18 CO*(g) → Re.sub.2 (CO).sub.10 (cr) + 8            COF(g)                                                                     2 × -920                                                                           18 × 564                                                                      -1651                                                                              8 × -172,                                                                     ΔH.sub.r *(298 K.) = -11,339 kJ                                          mol.sup.-1,                                            [II-677]                                                                           2 ReF.sub.5 (cr) + 20 CO(g) → Re.sub.2 (CO).sub.10 (cr) + 10            COF(g)                                                                     2 × -941                                                                           20 × -110                                                                     -1651                                                                              10 × - 172,                                                                   ΔH.sub.r.sup.0 (298 K.) = +711 kJ                                        mol.sup.-1,                                            [II-678]                                                                           2 ReF.sub.5 (cr) + 20 CO*(g) → Re.sub.2 (CO).sub.10 (cr) + 10           COF(g)                                                                     2 × -941                                                                           20 × 564                                                                      -1651                                                                              10 × -172,                                                                    ΔH.sub.r ((298 K.) = -12,769 kJ                                          mol.sup.-1,                                            [II-679]                                                                           2 ReF.sub.6 (cr) + 22 CO(g) → Re.sub.2 (CO).sub.10 (cr) + 12            COF(g)                                                                     2 × -1151                                                                          22 × -110                                                                     -1651                                                                              12 × -172,                                                                    ΔH.sub.r.sup.0 (298 K.) = +1007 kJ                                       mol.sup.-1                                             and                                                                            [II-680]                                                                           2 ReF.sub.6 (cr) + 22 CO*(g) → Re.sub.2 (CO).sub.10 (cr) + 12           COF(g)                                                                     2 × -1151                                                                          22 × 564                                                                      -1651                                                                              12 × -172,                                                                    ΔH.sub.r *(298 K.) = -13,821 kJ                  __________________________________________________________________________                             mol.sup.-1.                                       

Thus, we have the choice of four procedures for the volatilization of rhenium species:

O+F

(questionable if Re_(F) ₆ is present)

O+CO

CO*.

O. Group VIII B.

1. THERMODYNAMICS

Fe(CO)₅, Ni(CO)₄, RuO₄, OSO₄ and IrF₆ will volatilize spontaneously in the apparatus by [II-1]. The `times four` criterion for several species are:

    ______________________________________                                         FeF.sub.2          1264 kJ mol.sup.-1                                          FeF.sub.3           884                                                        CoF.sub.2          1264                                                        CoF.sub.3           368                                                        Co.sub.2 (CO).sub.8                                                                                264                                                        NiF.sub.2           936                                                        RuF5                408                                                        Ru.sub.3 (CO).sub.12                                                                               400                                                        Rh.sub.4 (CO).sub.12                                                                               404                                                        Rh.sub.6 (CO).sub.16                                                                               468                                                        Os.sub.3 (CO).sub.12                                                                               420                                                        Ir.sub.4 (CO).sub.12                                                                               420                                                        PtF.sub.4           548                                                        PtF.sub.6           184.                                                       ______________________________________                                    

                  TABLE II-18                                                      ______________________________________                                         GROUP VIII B.                                                                  THERMODYNAMIC DATA                                                             PART 1                                                                         ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES Fe          Co           Ni                                            ______________________________________                                         MO                                                                             (cr)     -272/-251   -238/-214   -240a/-212a                                   (l)      -250/-233                                                             (g)      +251/+218               +314a/--                                      M.sub.3 O.sub.4                                                                        -1121/-1017  -910/-795                                                 (cr)                                                                           M.sub.2 O.sub.3                                                                         -826/-744               -490a/--                                      (cr)                                                                           MCl      +251/+216   +193/+162    +182/+149                                    (g)                                                                            MCl.sub.2                                                                      (cr)     -342/-302   -313/-270    -305/-259                                    (l)      -311/-278   -272/-240    -234/-203                                    (g)      -141/-156    -94/-107    -74/-86                                      M.sub.2 Cl.sub.4     -351/-334                                                 (g)                                                                            MCl.sub.3                                                                      (cr)     -399/-334                                                             (l)      -362/-315                                                             (g)      -253/-248   -164/-155                                                 MF       +48/+14                                                               (g)                                                                            MF.sub.2                                                                       (cr)     -706/- 663  -672/-627   -651a/-604a                                   (l)      -675/-634   -638/-594   -618b/--                                      (g)      -390/-400   -356/-370   -417b/--                                      MF.sub.3                                                                       (cr)    -1042/-972   -790/-719                                                 (l)                  -740b/--                                                  (g)      -821/-813   -698b/--                                                  M.sub.2 (CO).sub.8                                                             (cr)                -1251c/--                                                  (g)                 -1185c/--                                                  M(CO).sub.n                                                                    (l)     n = 5   -766/              n = 4 -632/                                                 -697                     -589                                  (g)             -727/                    -602/                                                 -689                     -587                                  ______________________________________                                          (a, Ref. <B>; b, Ref. <II23>; c, Ref. <II15>)                            

                  TABLE II-19                                                      ______________________________________                                         GROUP VIII B.                                                                  THERMODYNAMIC DATA                                                             PART 2                                                                         ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES  Ru           Rh        Pd                                             ______________________________________                                         MO                                                                             (cr)                             -85a/--                                       (g)                    +385a/--                                                M.sub.2 O.sub.3        -343a/--                                                (cr)                                                                           MO.sub.2                                                                       (cr)      -305a/--                                                             (g)                    +184a/--                                                MO.sub.3  -78a/--                                                              (g)                                                                            MO.sub.4                                                                       (cr)      -239a/-152a                                                          (l)       -228a/-152a                                                          (g)       -184a/-140a                                                          MCL.sub.2                                                                      (cr)                            -199a/--                                       (g)                    +127a/--                                                MCl.sub.3                                                                      (cr)      -205a/--     -299a/--                                                (g)        -1a/--      +67a/--                                                 MCl.sub.4                                                                                -52a/                                                                (g)                                                                            MF.sub.2                        -469d/-494d                                    (cr)                                                                           MF.sub.5                                                                       (cr)      -893a/--                                                             (g)       -791a/--                                                             M.sub.3 (CO).sub.12                                                            (cr)     -1920c/--                                                             (g)      -1820c/--                                                             M.sub.4 (CO).sub.12                                                            (cr)                  -1825c/--                                                (g)                   -1724c/--                                                M.sub.6 (CO).sub.16                                                            (cr)                  -2418c/--                                                (g)                   -2301c/--                                                ______________________________________                                          (a, Ref <B>; c, Ref. <II15>; d, Ref. <II29>)                             

                  TABLE II-20                                                      ______________________________________                                         GROUP VIII B.                                                                  THERMODYNAMIC DATA                                                             PART 3                                                                         ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES  Os          Ir          Pt                                            ______________________________________                                         M.sub.3 O.sub.4                  -163a/--                                      (cr)                                                                           MO.sub.2                                                                       (cr)                  -274a/--                                                 (g)                              +172a/+167a                                   MO.sub.3  -284a/--     +8a/--                                                  (g)                                                                            MO.sub.4                                                                       (cr)      -394a/-305a                                                          (g)       -337a/-293a                                                          MCl                   -82a/--     -56a/--                                      (cr)                                                                           MCl.sub.2                        -123a/--                                      (cr)                                                                           MCl.sub.3                                                                                -190a/--    -246a/--   -182a/--                                      (cr)                                                                           MCl.sub.4                                                                      (cr)      -255a/--               -232a/--                                      (g)       -79a/--                -232a/--                                      MF.sub.4                                                                       (cr)                             -681e/--                                      (g)                              -544f/--                                      MF.sub.6                                                                       (cr)                  -580a/-462a                                                                               -722g/--                                      (g)                   -544a/-460a                                                                               -676g/--                                      M.sub.3 (CO).sub.12                                                            (cr      -1749c/--                                                             (g)      -1644c/--                                                             M.sub.4 (CO).sub.12                                                            (cr)                 -1820c/--                                                 (g)                  -1715c/--                                                 ______________________________________                                          (a, Ref. <B>; c, Ref. <II15>; e, Ref. <II30>; f, Ref. <II31>; g, Ref.          <II32>)                                                                  

2. BETA-DIKETONATES

For the main group elements we used as reagents O, O/NO₂, F, CH₃ and H. For GROUP VB we introduced CO. For the GROUP VIII B elements we find it useful to introduce the β-diketonyls. The βdiketones exist in two forms--the keto-form and the enol-form,

    ______________________________________                                         [II-681]                                                                       CH.sub.2               CH                                                      R.sub.1                                                                            C         C       R.sub.2 = R.sub.1                                                                     C       C     R.sub.2.                                 O       O                O     O                                                                 H                                                       KETO-FORM              ENOL-FORM                                               ______________________________________                                    

We shall consider here only three of the β-diketones:

R₁ =R₂ =CH₃, acetylacetone, Hacac, B.P.=140° C.

R₁ =CF₃, R₂ =CH₃, trifluoroacetylacetone, Htfac, B.P.=107° C.

R₁ =R₂ =CF₃, hexafluoroacetylacetone, Hhfac, B.P.=70° C.

(All of the data in this SECTION are from Ref. <II-33> unless specifically noted.)

For the reaction

    H-βdik(g)→H(g)+βdik·(g),         [II-682]

βdik. being the β-diketonyl radical, the ΔH_(r) is estimated to be 418 kJ mol⁻¹. If we add to [II-682],

    H(g)+X(g)→HX(g), ΔH.sub.r (683),              [II-683]

we obtain

    H-βdik(g)+X(g)→βdik.(g)+HX(g),[II-684]

    ΔH.sub.t (684)=418+ΔH.sub.t (684).             [II-684]

For ΔH_(t) (684)<0, we require that ΔH_(t) (683)<-418.

    ______________________________________                                         H(g) + H(g) → H.sub.2 (g)                                               218      218     0,      ΔH.sub.r.sup.0 (298 K.) = -436 kJ                                        mol.sup.-1,                                           H(g) + O(g) → OH(g)                                                     218      249     39,     ΔH.sub.r.sup.0 (298 K.) = -428 kJ                                        mol.sup.-1                                            and                                                                            H(g) + F(g) → HF(g)                                                     218      79      -272,   ΔH.sub.r.sup.0 (298 K.) = -569 kJ                                        mol.sup.-1.                                           ______________________________________                                    

Thus, we find that all three reagents are effective, but that monofluorine is the preferred reagent.

The enthalpies of formation of the three gaseous β-diketones are

    Hacac(g), ΔH.sub.r.sup.0 (298K)=-383kJ mol.sup.-

    Htfac(g), ΔH.sub.f.sup.0 (298K)=-1014kJ mol.sup.-1

    Hhfac(g), ΔH.sub.f.sup.0 (298K)=-1643kJ mol.sup.-1.

By [II-682]

    ______________________________________                                         418 = ΔH.sub.f.sup.0 {βdik · (g)} + ΔH.sub.f.sup     .0 {H(g)} - ΔH.sub.f.sup.0 {H - βdik(g)}                            or                                                                             ΔH.sub.f.sup.0{βdik · (g)} =                                         418 - ΔH.sub.f.sup.0 {H(g)} + ΔH.sub.f.sup.0 {H -                  βdik(g)} =                                                                418 - 218 + ΔH.sub.f.sup.0 {H - βdik(g)} =                          200 + ΔH.sub.f.sup.0 {H - βdik(g)}                        ______________________________________                                    

and

    ΔH.sub.f.sup.0 {acac(g)}=-183kJ mol.sup.-1

    ΔH.sub.f.sup.0 {tfac(g)}=-814kJ mol.sup.-1

    ΔH.sub.f.sup.0 {hfac(g)}=-1443kJ mol.sup.-1.

We now consider the reaction

    M(cr)+nβdik(g)→M(βdik).sub.n (cr),        [II-685]

    ΔH.sub.r.sup.0 (685)=ΔH.sub.f.sup.0 {M(βdik).sub.n (cr)}-nΔH.sub.f.sup.0 {βdik(g)}.

By the `times four` criterion we require that

    ______________________________________                                         [II-686]                                                                               4 ΔH.sub.sub.sup.0 {M(βdik).sub.n }<                                               -ΔH.sub.r.sup.0 (685)                                                    < -ΔH.sub.f.sup.0 {M(βdik).sub.n (cr)}                              +n ΔH.sub.f.sup.0 {βdik(g)}.                 ______________________________________                                    

For M(acac)_(n) we have all the necessary data for three cases:

    ______________________________________                                         Cr:          4 ×                                                                             123 .sub.<.sup.?  1565 + 3 × -183                                        492 > 1016                                                 Al:          4 ×                                                                             120 .sub.<.sup.?  1798 + 3 × -183                                        480 < 1249                                                 Cu:          4 ×                                                                             110 .sub.<.sup.?  810 + 2 × -183                                         440 < 444.                                                 ______________________________________                                    

Thus, we find that acac(g) is an effective volatilizing reagent for both Cr and Al and is borderline for Cu. (It should be noted that Ref. <II-33> gives two values for ΔH_(f) ⁰ {Cu(acac)₂ (cr)}, -809.9 and -782.4 kJ mol⁻¹. The -809.9 kJ mol⁻¹ is the more recent value.)

For M(tfac)_(n) we have all the necessary data for two cases:

    ______________________________________                                         Be:          4 ×                                                                             88 .sub.<.sup.?  2498 - 2 × 814                                          352 < 870                                                  Al:          4 ×                                                                             108 .sub.<.sup.?  3696 - 3 × 814                                         432 < 1254.                                                ______________________________________                                    

Again we find that β-dik(g) is an effective volatilizing reagent.

For M(Hfac)_(n) we have data only for Cr and Cu, but the data are not complete. We have the enthalpies of sublimation, but not the enthalpies of formation for either the crystalline or gaseous states. We can, however, roughly estimate these values.

    M(βdik).sub.n (g)→M(g)+nβdik.(g),[II-68]

    ΔH.sub.r.sup.0 (687)=2nD(M-O),

where D(M-O) is the average mean metal oxygen dissociation enthalpy. For Cr (hfac)₃, D(M-O)=238 kJ mol⁻¹, and for Cu (hfac)₂, D(M-O)=163 kJ mol⁻¹. (It should be noted that both of these values are given as ±11 kJ mol⁻¹. )

For Cr,

    ΔH.sub.f.sup.0 (687)=6×238=ΔH.sub.f.sup.0 {Cr(g)}+3ΔH.sub.f.sup.0 {hfac(g)}-ΔH.sub.f.sup.0 {Cr(hfac).sub.3 (g)}

    ______________________________________                                              ΔH.sub.f.sup.0 {Cr(hfac).sub.3 (g)} =                                                   -6 × 238 + 397 + 3 × -1443                          =              -5360 kJ mol.sup.-,                                        and                                                                                 ΔH.sub.f.sup.0 {Cr(hfac).sub.3 (cr)} =                                                  5360 - 112                                                      =              -5472 kJ mol.sup.-1.                                       ______________________________________                                    

Applying these numbers to [II-686] we have

    ______________________________________                                                 4 × 112                                                                         .sub.<.sup.? 5472 + 3 × -1443                                     448    <1143.                                                          ______________________________________                                    

For Cu,

    ______________________________________                                              ΔH.sub.r (687) = 4 × 163 =                                                        ΔH.sub.f.sup.0 {cr(g)} + 2 ΔH.sub.f.sup.0                          (hfac) -                                                                       ΔH.sub.f.sup.0 {Cu(hfac).sub.2 (g)},                 or                                                                                  ΔH.sub.f.sup.0 {Cu(hfac).sub.2 (g)} =                                                   -4 × 163 + 338 + 2 × 1443 =                                        -3200 kJ mol.sup.-1,                                       and                                                                                 ΔH.sub.f.sup.0 {Cu(hfac).sub.2 (cr)} =                                                  -3200 - 111 =                                                                  -3311 kJ mol.sup.-1.                                       ______________________________________                                    

Applying these numbers to [II-686] we have

    ______________________________________                                                 4 × 111                                                                         .sub.<.sup.? 3311 + 2 × -1443                                     444    < 425.                                                          ______________________________________                                    

If we had taken the extreme value for D(Cu-O)=174 kJ mol⁻¹, the inequality would have read

    ______________________________________                                                 4 × 111                                                                         .sub.<.sup.? 355 + 2 × -1443                                      444    < 469.                                                          ______________________________________                                    

Thus, the copper case is borderline. Under the conditions of the Apparatus the procedure is effective.

3. IRON

    __________________________________________________________________________     [II-688]                                                                           Fe(cr) + O(g) → FeO(cr)                                             0         249   -272,  ΔH.sub.r.sup.0 (298 K.) = -521 kJ                                        mol.sup.-1                                              0         232   -251,  ΔG.sub.r.sup.0 (298 K.) = -483 kJ                                        mol.sup.-1,                                             [II-689]                                                                           FeO(cr) + 1/3 O(g) → 1/3 Fe.sub.3 O.sub.4 (cr)                      -272      1/3 × 249                                                                      1/3 × -1121,                                                                    ΔH.sub.r.sup.0 (298 K.) = -185 kJ                                        mol.sup.-1                                              -251      1/3 × 232                                                                      1/3 × -1017,                                                                    ΔG.sub.r.sup.0 (298 K.) = -165 kJ                                        mol.sup.-1                                              and                                                                            [II-690]                                                                           1/3 Fe.sub.3 O.sub.4 cr) + 1/6 O(g) → 1/2 Fe.sub.2 O.sub.3              (cr)                                                                       1/3 × -1121                                                                        1/6 × 249                                                                      1/2 × -826,                                                                     ΔH.sub.r.sup.0 (298 K.) = -81 kJ mol.sup.-1       1/3 × - 1017                                                                       1/6 × 232                                                                      1/2 × -744,                                                                     ΔG.sub.r.sup.0 (298 K.) = -72 kJ                  __________________________________________________________________________                            mol.sup.-1.                                        

Since the `times four` criterion for the melting of the ferrous oxide is 88 kJ mol⁻¹, [II-688] will yield the liquid product. Whether the reaction will stop with [II-689] or continue to [II-690] is uncertain. For our present purposes, however, it does not make any difference.

    __________________________________________________________________________     [II-691]                                                                           FeCl.sub.2 (cr) + 5 O(g) → FeO(cr) + 2 ClO.sub.2 (g)                -342    5 × 249                                                                       -272  2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -971 kJ                                        mol.sup.-1                                             -302    5 × 232                                                                       -251  2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -869 kJ                                        mol.sup.-1,                                            [II-692]                                                                           FeCl.sub.3 (cr) + 7 O(g) → FeO(cr) + 3 ClO.sub.2 (g)                -399    7 × 249                                                                       -272  3 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1310 kJ                                       mol.sup.-1                                             -334    7 × 232                                                                       -251  3 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1181 kJ                                       mol.sup.-1,                                            [II-693]                                                                           FeF.sub.2 (cr) + 5 O(g) → FeO(cr) + 2 FO.sub.2 (g)                  -706    5 × 249                                                                       -270  2 × 13,                                                                       Δ H.sub.r.sup.0 (298 K.) = -783 kJ                                       mol.sup.-1                                             -663    5 × 232                                                                       -251  2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -694 kJ                                        mol.sup.-1                                             and                                                                            [II-694]                                                                           FeF.sub.3 (cr) + 7 O(g) → FeO(cr) + 3 FO.sub.2 (g)                  -1042   7 × 249                                                                       -272  3 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -934 kJ                                        mol.sup.-1                                             -972    7 × 232                                                                       -251  3 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -822 kJ                                        mol.sup.-1,                                            [II-695]                                                                           Fe(cr) + 2 F(g) → FeF.sub.2 (cr)                                    0       2 × 79                                                                       -706,                                                                               ΔH.sub.r.sup.0 (298 K.) = -864 kJ mol.sup.-1            0       2 × 62                                                                       -663,                                                                               ΔG.sub.r.sup.0 (298 K.) = -787 kJ mol.sup.-1,           [II-696]                                                                           FeF.sub.2 (cr) + F(g) → FeF.sub.3 (cr)                              - 706   79  -1042,                                                                              ΔH.sub.r.sup.0 (298 K.) = -415 kJ mol.sup.-1            -663    62  -972,                                                                               ΔG.sub.r.sup.0 (298 K.) = -371 kJ mol.sup.-1,           [II-697]                                                                           FeF.sub.2 (cr) + F*(g) → FeF.sub.3 (cr)                             -706    245 -1042,                                                                              ΔH.sub.r *(298 K.) = -581 kJ mol.sup.-1,                [II-698]                                                                           FeO(cr) + 5 F(g) → FeF.sub.3 (cr) + OF.sub.2 (g)                    -272    5 × 79                                                                        -1042 24,  ΔH.sub.r.sup.0 (298 K.) = -1141 kJ                                       mol.sup.-1                                             -251    5 × 62                                                                        -972  42,  ΔG.sub.r.sup.0 (298 K.) = -989 kJ                                        mol.sup.-1,                                            [II-699]                                                                           Fe.sub.3 O.sub.4 (cr) + 17 F(g) → 3 FeF.sub.3 (cr) + 4                  OF.sub.2 (g)                                                               -1121   17 × 79                                                                       3 × -1042                                                                      4 × 24,                                                                       ΔH.sub. r.sup.0 (298 K.) = -3252 kJ                                      mol.sup.-1                                             -1017   17 × 62                                                                       3 × -972                                                                       4 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -2785 kJ                                       mol.sup.-1                                             and                                                                            [II-700]                                                                           Fe.sub.2 O.sub.3 (cr) + 12 F(g) → 2 FeF.sub.3 (cr) + 3                  OF.sub.2 (g)                                                               -826    12 × 79                                                                       2 × -1042                                                                      3 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2134 kJ                                       mol.sup.-1                                             -744    12 × 62                                                                       2 × -972                                                                       3 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1818 kJ                                       mol.sup.-1.                                            __________________________________________________________________________

Thus, O+F is an effective procedure. By virtue of [II-697] even excited state monofluorine alone is not an effective procedure.

    __________________________________________________________________________     [II-701]                                                                           Fe(cr) + 5 CO(g) → Fe(CO).sub.5 (l)                                 0     5 × -110                                                                      -766,                                                                              ΔH.sub.r.sup.0 (298 K.) = -216 kJ mol.sup.-1              0     5 × -137                                                                      -697,                                                                              ΔG.sub.r.sup.0 (298 K.) = -12 kJ mol.sup.-1,              [II-702]                                                                           FeO(cr) + 6 CO(g) → Fe(CO).sub.5 (l) + CO.sub.2 (g)                 -272    6 × -110                                                                       -766  -394, ΔH.sub.r.sup.0 (298 K.) = -228 kJ                                        mol.sup.-1                                           -251    6 × -137                                                                       -697  -394, ΔG.sub.r.sup.0 (298 K.) = -18 kJ                                         mol.sup.-1,                                          [II-703]                                                                           Fe.sub.3 O.sub.4 (cr) + 19 CO(g) → Fe(CO).sub.5 (l) + 4                 CO.sub.2 (g)                                                               -1121   19 × -110                                                                      3 × -766                                                                       4 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -663 kJ                                        mol.sup.-1                                           -1017   19 × -137                                                                      3 × -697                                                                       4 × -394,                                                                      ΔG.sub.r.sup.0 (298 K.) = -47 kJ                                         mol.sup.-1,                                          [II-704]                                                                           Fe.sub.2 O.sub.3 (cr) + 13 CO(g) → 2 Fe(CO).sub.5 (l) + 3               CO.sub.2 (g)                                                               -826    13 × -110                                                                      2 × -766                                                                       3 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -458 kJ                                        mol.sup.-1                                           -744    13 × -137                                                                      2 × -697                                                                       3 × -394,                                                                      ΔG.sub.r.sup.0 (298 K.) = -51 kJ                                         mol.sup.-1,                                          [II-705]                                                                           FeCl.sub.2 (cr) + 7 CO(g) → Fe(CO).sub.5 (l) + 2 COCl(g)            -342    7 × -110                                                                       -766  2 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +220 kJ                                        mol.sup.-1                                           -302    7 × -137                                                                       -697  2 × -77,                                                                       ΔG.sub. r.sup.0 (298 K.) = +410 kJ                                       mol.sup.-1,                                          [II-706]                                                                           FeCl.sub.2 (cr) + 7 CO*(g) → Fe(CO).sub.5 (l) + 2 COCl(g)           -342    7 × 564                                                                        -766  2 × -63,                                                                       ΔH.sub.r *(298 K.) = -4498 kJ                                            mol.sup.-1,                                          [II-707]                                                                           FeCl.sub.3 (cr) + 8 CO*(g) → Fe(CO).sub.5 (l) + 3 COCl(g)           -399    8 × 564                                                                        -766  3 × -63,                                                                       ΔH.sub.r *(298 K.) = -5068 kJ                                            mol.sup.-1,                                          [II-708]                                                                           FeF.sub.2 (cr) + 7 CO*(g) → Fe(CO).sub.5 (l) + 2 COF(g)             -706    7 × 564                                                                        -766  2 × -172,                                                                      ΔH.sub.r *(298 K.) = -4352 kJ mol.sup.-1       and                                                                            [II-709]                                                                           FeF.sub.3 (cr) + 8 CO*(g) → Fe(CO).sub.5 (l) + 3 COF(g)             -1042   8 × 564                                                                        -766  3 × -172,                                                                      ΔH.sub.r *(298 K.) = -4752 kJ                  __________________________________________________________________________                               mol.sup.-1.                                     

Thus, we have the choice of three procedures for the volatilization of iron species:

O+F

O+CO

CO*

4. COBALT

    ______________________________________                                         [II-710]                                                                               Co(cr) + O(g) → CoO(cr)                                         0            249       -238, ΔH.sub.r.sup.0 (298 K.) =                                          -487 kJ mol.sup.-1                                      0            232       -214, ΔG.sub.r.sup.0 (298 K.) =                                          -246 kJ mol.sup.-1                                      and                                                                            [II-711]                                                                               CoO(cr) + 1/3 O(g) → 1/3 CO.sub.3 O.sub.4 (cr)                  -238         1/3 × 249                                                                          1/3 × -910, ΔH.sub.r.sup.0 (298 K.) =                              -148 kJ mol.sup.-1                                      -214         1/3 × 232                                                                          1/3 × -795, ΔG.sub.r.sup.0 (298 K.) =                              -128 kJ mol.sup.-1.                                     ______________________________________                                    

The oxides CO₂ O₃ and CoO₂ are also known, but we have no thermodynamic data on them.

    ______________________________________                                         [II-712]                                                                             CoCl.sub.2 (cr) + 5 O(g) → CoO(cr) + 2 ClO.sub.2 (g)              -313      5 × 249                                                                           -238     2 × 102, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -966 kJ mol.sup.-1                                 -270      5 × 232                                                                           -214     2 × 120, ΔG.sub.r.sup.0 (298 K.)                                   =                                                                              -864 kJ mol.sup.-1,                                [II-713]                                                                             CoF.sub.2 (cr) + 5 O(g) → CoO(cr) + 2 FO.sub.2 (g)                -672      5 × 249                                                                           -238     2 × 13, ΔH.sub.r.sup.0 (298 K.)                                    =                                                                              -785 kJ mol.sup.-1                                 -627      5 × 232                                                                           -214     2 × 27, ΔG.sub.r.sup.0 (298 K.)                                    =                                                                              -693 kJ mol.sup.-1                                 and                                                                            [II-714]                                                                             CoF.sub.3 (cr) + 7 O(g) → CoO(cr) + 3 FO.sub.2 (g)                -790      7 ×  249                                                                          -238     3 × 13, ΔH.sub.r.sup.0 (298 K.)                                    =                                                                              -1152 kJ mol.sup.-1                                -719      7 × 232                                                                           -214     3 × 27, ΔG.sub.r.sup.0 (298 K.)                                    =                                                                              -1038 kJ mol.sup.-1.                               [II-715]                                                                             Co(cr) + 2 F(g) → CoF.sub.2 (cr)                                  0         2 × 79                                                                            -672, ΔH.sub.r.sup.0 (298 K.) =                                          -830 kJ mol.sup.-1                                          0         2 × 62                                                                            -627, ΔG.sub.r.sup.0 (298 K.) =                                          -751 kJ mol.sup.-1,                                         [II-716]                                                                             Co(cr) + 2 F*(g) → CoF.sub.2 (cr)                                 0         2 × 245                                                                           -672, ΔH.sub.r *(298 K.) =                                               -1162 kJ mol.sup.-1,                                        [II-717]                                                                             CoF.sub.2 (cr) + F(g) → CoF.sub.3 (cr)                            -672      79       -790, ΔH.sub.r.sup.0 (298 K.) =                                          -197 kJ mol.sup.-1                                          -627      62       -719, ΔG.sub.r.sup.0 (298 K.) =                                          -154 kJ mol.sup.-1                                          and                                                                            [II-718]                                                                             CoF.sub.2 (cr) + F*(g) → CoF.sub.3 (cr)                           -672      245      -790, ΔH.sub.r *(298 K.) =                                               -363 kJ mol.sup.-1.                                         ______________________________________                                    

Since the `times four` criterion for the trifluoride is 368 kJ mol⁻¹, [II-718] is marginally effective in the volatilization of the trifluoride. It is, therefore, not advisable to depend on the F* procedure.

    __________________________________________________________________________     [II-719]                                                                           CoO(cr) + 4 F(g) → CoF.sub.2 (cr) + OF.sub.2 (g)                    -238    4 × 79                                                                        -672 24,  ΔH.sub.r.sup.0 (298 K.) = -726 kJ                                        mol.sup.-1                                              -214    4 × 62                                                                        -627 42,  ΔG.sub.r.sup.0 (298 K.) = -619 kJ                                        mol.sup.-1,                                             [II-720]                                                                           CoO(cr) + 4 F*(g) → CoF.sub.2 (cr) + OF.sub.2 (g)                   -238    4 × 245                                                                       -672 24,  ΔH.sub.r *(298 K.) = -1390 kJ mol.sup.-1,         [II-721]                                                                           CoO(cr) + 5 F(g) → CoF.sub.3 (cr) + OF.sub.2 (g)                    -238    5 × 79                                                                        -790 24,  ΔH.sub.r.sup.0 (298 K.) = -923 kJ                                        mol.sup.-1                                              -214    5 × 62                                                                        -719 42,  ΔG.sub.r.sup.0 (298 K.) = -773 kJ                                        mol.sup.-1,                                             [II-722]                                                                            Co.sub.3 O.sub.4 (cr) + 14 F(g) → 3 CoF.sub.2 (cr) + 4                 OF.sub.2 (g)                                                               -910    14 × 79                                                                       3 × -672                                                                      4 × 29,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2116 kJ                                       mol.sup.-1                                              -795    14 × 62                                                                       3 × -627                                                                      4 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -1786 kJ                                       mol.sup.-1,                                             [II-723]                                                                           Co.sub.3 O.sub.4 (cr) + 14 F*(g) → 3 CoF.sub.2 (cr) + 4                 OF.sub.2 (g)                                                               -910    14 × 245                                                                      3 × -672                                                                      4 × 24,                                                                       ΔH.sub.r *(298 K.) = -4440 kJ mol.sup.-1          and                                                                            [II-724]                                                                           Co.sub.3 O.sub.4 (cr) + 17 F(g) → 3 CoF.sub.3 (cr) + 4                  OF.sub.2 (g)                                                               -910    17 × 79                                                                       3 × -790                                                                      4 × 24,                                                                       ΔH.sub.r.sup.0 (298 K.) =  -2707 kJ                                      mol.sup.-1                                              -795    17 × 62                                                                       3 × -719                                                                      4 × 42,                                                                       ΔG.sub.r.sup.0 (298 K.) = -2248 kJ                                       mol.sup.-1.                                             __________________________________________________________________________

Thus, O+F* is an effective procedure as is O+F is sufficient monofluorine is present to ensure that all of the fluoride formed is the trifluoride

    __________________________________________________________________________     [II-725]                                                                           2 Co(cr) + 8 CO(g) → CO.sub.2 (CO).sub.8 (cr)                       0         8 × -110                                                                       -1251,                                                                             ΔH.sub.r.sup.0 (298 K.) = -371 kJ mol.sup.-1,        [II-726]                                                                           2 CoO(cr) + 10 CO(g) → Co.sub.2 (CO).sub.8 (cr) + 2 CO.sub.2            (g)                                                                        2 × -238                                                                           10 × -110                                                                      -1251  2 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -463 kJ                                        mol.sup.-1                                        and                                                                            [II-727]                                                                           Co.sub.3 O.sub.4 (cr) + 16 CO(g) → 1.5 Co.sub.2 (CO).sub.8              (cr) + 4 CO.sub.2 (g)                                                      -910      16 × 110                                                                       1.5 × -1151                                                                     4 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -782 kJ                                        mol.sup.-1.                                       __________________________________________________________________________

Thus, O+CO is an effective procedure.

    __________________________________________________________________________     [II-728]                                                                           2 CoCl.sub.2 (cr) + 12 CO(g) → Co(CO).sub.8 (cr) + 4 COCl(g)        2 × -313                                                                           12 × -110                                                                      -1251                                                                              4 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +443 kJ                                        mol.sup.-1,                                          [II-729]                                                                           2 CoCl.sub.2 (cr) + 12 CO*(g) → Co.sub.2 (CO).sub.8 (cr) + 4            COCl(g)                                                                    2 × -313                                                                           12 × 564                                                                       -1251                                                                              4 × -63,                                                                       ΔH.sub.r *(298 K.) = -7645 kJ                                            mol.sup.-1,                                          [II-730]                                                                           2 CoF.sub.2 (cr) + 12 CO(g) → Co.sub.2 (CO).sub.8 (cr) + 4              COF(g)                                                                     2 × -672                                                                           12 × -110                                                                      -1251                                                                              4 × -172,                                                                      ΔH.sub.r.sup.0 (298 K.) = +725 kJ                                        mol.sup.-1,                                          [II-731]                                                                           2 CoF.sub.2 (cr) + 12 CO*(g) → Co.sub.2 (CO).sub. 8 (cr) + 4            COF(g)                                                                     2 × -672                                                                           12 × 564                                                                       -1251                                                                              4 × -172,                                                                      ΔH.sub.r *(298 K.) = -7363 kJ                                            mol.sup.-1,                                          [II-732]                                                                           2 CoF.sub.3 (cr) + 14 CO(g) → Co.sub.2 (CO).sub.8 (cr) + 6              COF(g)                                                                     2 × -790                                                                           14 × -110                                                                      -1251                                                                              6 × -172,                                                                      ΔH.sub.r.sup.0 (298 K.) = +837 kJ                                        mol.sup.-1                                           and                                                                            [II-733]                                                                           2 CoF.sub.3 (cr) + 14 CO*(g) → Co.sub.2 (CO).sub.8 (cr) + 6             COF(g)                                                                     2 × -790                                                                           14 × 564                                                                       -1251                                                                              6 × -172,                                                                      ΔH.sub.r *(298 K.) = -8599 kJ                  __________________________________________________________________________                               mol.sup.-1.                                     

Thus, the choices of procedures for the volatilization of cobalt species are

O+F (?)

)+F*

O+CO

CO*.

5. NICKEL

    __________________________________________________________________________     [II-734]                                                                           Ni(cr) + O(g) → NiO(cr)                                             0       249   -240,  ΔH.sub.r.sup.0 (298 K.) = -489 kJ mol.sup.-1        0       232   -212,  ΔG.sub.r.sup.0 (298 K.) = -444 kJ mol.sup.-1,       [II-735]                                                                           NiO(cr) + 0.5 O(g) → 0.5 Ni.sub.2 O.sub.3 (cr)                      -240    0.5 × 249                                                                      0.5 × -490,                                                                     ΔH.sub.r.sup.0 (298 K.) = -130 kJ mol.sup.-1,       [II-736]                                                                           NiCl.sub.2 (cr) + 5 O(g) → NiO(cr) + 2 ClO.sub.2 (g)                -305    5 × 249                                                                        -240  2 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -976 kJ                                        mol.sup.-1                                           -259    5 × 232                                                                        -212  2 × 120,                                                                       ΔG.sub.r.sup.0 (298 K.) = -873 kJ                                        mol.sup.-1                                           and                                                                            [II-737]                                                                           NiF.sub.2 (cr) + 5 O(g) → NiO(cr) +  2 FO.sub.2 (g)                 -651    5 × 249                                                                        -240  2 × 13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -808 kJ                                        mol.sup.-1,                                          -604    5 × 232                                                                        -212  2 × 27,                                                                        ΔG.sub.r.sup.0 (298 K.) = -714 kJ                                        mol.sup.-1,                                          [II-738]                                                                           Ni(cr) + 2 F(g) → NiF.sub.2 (cr)                                    0       2 × 79                                                                         -651,  ΔH.sub.r.sup.0 (298 K.) = -809 kJ mol.sup.-1        0       2 × 62                                                                         -604,  ΔG.sub.r.sup.0 (298 K.) = -728 kJ mol.sup.-1,       [II-739]                                                                           Ni(cr) + 2 F*(g) → NiF.sub.2 (cr)                                   0       2 × 245                                                                        -651,  ΔH.sub.r *(298 K.) = -1141 kJ mol.sup.-1,           [II-740]                                                                           NiO(cr) + 4 F(g) → NiF.sub.2 (cr) + OF.sub.2 (g)                    -240    4 × 79                                                                         -651  24,    ΔH.sub.r.sup.0 (298 K.) = -703 kJ                                       mol.sup.-1                                           -212    4 × 62                                                                         -604  42,   ΔG.sub.r.sup.0 (298 K.) = -598 kJ                                        mol.sup.-1,                                          [II-741]                                                                           NiO(cr) + 4 F*(g) → NiF.sub.2 (cr) + OF.sub.2 (g)                   -240    4 × 245                                                                        -651  24,   ΔH.sub.r *(298 K.) = -1367 kJ                                            mol.sup.-1,                                          [II-742]                                                                           Ni.sub.2 O.sub.3 (cr) + 10 F(g) → 2 NiF.sub.2 (cr) + 3                  OF.sub.2 (g)                                                               -490    10 × 79                                                                        2 × -651                                                                       3 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1530 kJ                                       mol.sup.-1,                                          [II-743]                                                                           Ni.sub.2 O.sub.3 (cr) + 10 F*(g) → 2 NiF.sub.2 (cr) = 3                 OF.sub.2 (g)                                                               -490    10 × 245                                                                       2 × -651                                                                       3 × 24,                                                                        ΔH.sub.r *(298 K.) =  -3190 kJ                                           mol.sup.-1,                                          [II-744]                                                                           NiCl.sub.2 (cr) + 8 F(g) → NiF.sub.2 (cr) + 2 ClF.sub.3 (g)         -305    8 × 79                                                                         -651  2 × -159,                                                                      ΔH.sub.r.sup.0 (198 K.) = -1296 kJ                                       mol.sup.-1                                           -259    8 × 62                                                                         -604  2 × -119,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1079 kJ                                       mol.sup.-1,                                          [II-745]                                                                           Ni(cr) + 4 CO(g) → Ni(CO).sub.4 (l)                                 0       4 × 110                                                                        -632,  ΔH.sub.r.sup.0 (298 K.) = -192 kJ mol.sup.-1        0       4 × -137                                                                       -589,  ΔG.sub.r.sup.0 (298 K.) = -41 kJ mol.sup.-1,        [II-746]                                                                           NiO(cr) + 5 CO(g) → Ni(CO).sub.4 (l) + CO.sub.2 (g)                 -240    5 × -110                                                                       -632  -394, ΔH.sub.r.sup.0 (298 K.) = -236 kJ                                        mol.sup.-1                                           -212    5 × -137                                                                       -589  -394, ΔG.sub.r.sup.0 (298 K.) = -86 kJ                                         mol.sup.-1,                                          [II-747]                                                                           Ni.sub.2 O.sub.3 (cr) + 11 CO(g) → 2 Ni(CO).sub.4 (l) + 3               CO.sub.2 (g)                                                               -490    11 × -110                                                                      2 × -632                                                                       3 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -746 kJ                                        mol.sup.-1,                                          [II-748]                                                                           NiCl.sub.2 (cr) + 10 CO(g) → Ni(CO).sub.4 (l) + 2 COCl(g)           -305    10 × -110                                                                      -632  2 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +647 kJ                                        mol.sup.-1,                                          -259    10 × -137                                                                      -589  2 × -77,                                                                       ΔG.sub.r.sup.0 (298 K.) = +886 kJ                                        mol.sup.-1,                                          [II-749]                                                                           NiCl.sub.2 (cr) + 10 CO*(g) → Ni(CO).sub.4 (l) + 2 COCl(g)          -305    10 × 564                                                                       -632  2 × -63,                                                                       ΔH.sub.r *(298 K.) = -6093 kJ                                            mol.sup.-1,                                          [II-750]                                                                           NiF.sub.2 (cr) + 10 CO(g) → Ni(CO).sub.4 (l) + 2 COF(g)             -651    10 × -110                                                                      -632  2 × -172,                                                                      ΔH.sup.0 (298 K.) = +775 kJ mol.sup.-1         -604    10 × -137                                                                      -589  2 × -183,                                                                      ΔG.sub.r.sup.0 (298 K.) = +1019 kJ                                       mol.sup.-1                                           and                                                                            [II-751]                                                                           NiF.sub.2 (cr) + 10 CO*(g) → Ni(CO).sub.4 (l) + 2 COF(g)            -651    10 × 564                                                                       -632  2 × -172,                                                                      ΔH.sub.r *(298 K.) = -5975 kJ                  __________________________________________________________________________                               mol.sup.-1.                                     

Thus, we have the choice of four procedures for the volatilization of nickel species:

O+F*

F* (in the absence of NiF₂)

O+CO

CO*.

6. RUTHENIUM

    ______________________________________                                         [II-752]                                                                               Ru(cr) + 2 O(g) → RuO.sub.2 (cr)                                0            2 × 249                                                                             -305, ΔH.sub.r.sup.0 (298 K.) =                                          -803 kJ mol.sup.-1,                                    [II-753]                                                                               RuO.sub.2 (cr) + O(g) → RuO.sub.3 (g)                           -305         249        -78, ΔH.sub.r.sup.0 (298 K.) =                                           -22 kJ mol.sup.-1                                      and                                                                            [II-754]                                                                               RuO.sub.2 (cr) + 2 O(g) → RuO.sub.4 (cr)                        -305         2 × 249                                                                             -239, ΔH.sub.r.sup.0 (298 K.) =                                          -432 kJ mol.sup.-1.                                    ______________________________________                                    

The dioxide crystallizes in the rutile structure. Each ruthenium atom is bonded to six oxygens octahedrally, and each oxygen is bonded to three ruthenium atoms. In the tetroxide, however, each ruthenium atom is bonded to four oxygen atoms tetrahedrally, and each oxygen atom is bonded to only one ruthenium atom <II-34>. Reaction [II-754] is, therefore, expected to be slow unless the dioxide is amorphous. Thus, it cannot be relied as a means of volatilizing the dioxide.

    ______________________________________                                         [II-755]                                                                             RuCl.sub.3 (cr) + 10 O(g) → RuO.sub.4 (cr) + 3 ClO.sub.2                (g)                                                                      -205       10 × 249                                                                          -239    3 × 102, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -2218 kJ mol.sup.-1,                               and                                                                            [II-756]                                                                             RuF.sub.5 (cr) + 14 O(g) → RuO.sub.4 (cr) + 5 FO.sub.2 (g)        -893       14 × 249                                                                          -239     5 × 13, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -2767 kJ mol.sup.-1.                               ______________________________________                                    

Thus, with the caveat that the rate of removal of the dioxide may be quite slow monoxygen can be an effective volatilizing reagent for ruthenium species.

    __________________________________________________________________________     [II-757]                                                                           Ru(cr) + 5 F(g) → RuF.sub.5 (cr)                                    0     5 × 79                                                                          -893, ΔH.sub.r.sup.0 (298 K.) = -1288 kJ mol.sup.-1,        [II-758]                                                                           RuO.sub.2 (cr) + 9 F(g) → RuF.sub.5 (cr) + 2 OF.sub.2 (g)           -305      9 × 79                                                                         -893                                                                               2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1251 kJ                                       mol.sup.-1                                           and                                                                            [II-759]                                                                           RuCl.sub.3 (cr) + 14 F(g) → RuF.sub.5 (cr) + 3 ClF.sub.3 (g)        -205      14 × 79                                                                        -893                                                                               3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2271 kJ                                       mol.sup.-1,                                          [II-760]                                                                           3 Ru(cr) + 12 CO(g) → Ru.sub.3 (CO).sub.12 (cr)                     0     12 × -110                                                                      -1920, ΔH.sub.r.sup.0 (298 K.) = -600 kJ mol.sup.-1,         [II-761]                                                                           3 RuO.sub.2 (cr) + 18 CO(g) → Ru.sub.3 (CO).sub.12 (cr) + 6             CO.sub.2 (g)                                                               3 × -305                                                                           18 × -110                                                                      -1920                                                                              6 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1389 kJ                                       mol.sup.-1,                                          [II-762]                                                                           3 RuCl.sub.3 (cr) + 21 CO(g) → Ru.sub.3 (CO).sub.12 (cr) + 9            COCl(g)                                                                    3 × -205                                                                           21 × -110                                                                      -1920                                                                              9 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +438 kJ                                        mol.sup.-1,                                          [II-763]                                                                           3 RuCl.sub.3 (cr) + 21 CO*(g) → Ru.sub.3 (CO).sub.12 (cr) + 9           COCl(g)                                                                    3 × -205                                                                           21 × 564                                                                       -1920                                                                              9 × -63,                                                                       ΔH.sub.r *(298 K.) = -13,716 kJ                                          mol.sup.-1,                                          [II-764]                                                                           3 RuF.sub.5 (cr) + 27 CO(g) → Ru.sub.3 (CO).sub.12 + 15                 COF(g)                                                                     3 × -893                                                                           27 × -110                                                                      -1920                                                                              15 × -172,                                                                     ΔH.sub.r.sup.0 (298 K.) = +1149 kJ                                       mol.sup.-1                                           and                                                                            [II-765]                                                                           3 RuF.sub.5 (cr) + 27 CO*(g) → Ru.sub.3 (CO).sub.12 + 15                COF(g)                                                                     3 × -893                                                                           27 × 564                                                                       -1920                                                                              15 × -172,                                                                     ΔH.sub.r *(298 K.) = -17,049                   __________________________________________________________________________                               mol.sup.-1.                                     

Thus, the choices of procedures for the volatilization of ruthenium species are

O (?)

O+F

F (in the absence of RuF₅)

O+CO

CO*.

7. RHODIUM

In the absence of data on the rhodium fluorides we can make no judgment relative to the efficacy of monofluorine.

    ______________________________________                                         [II-766]                                                                             Rh(cr) + O(g) → RhO(g)                                            0           249        385, ΔH.sub.r.sup.0 (298 K.) =                                           +136 kJ mol.sup.-1,                                     [II-767]                                                                             Rh(cr) + 1.5 O(g) → 0.5 Rh.sub.2 O.sub.3 (cr)                     0           1.5 × 249                                                                           0.5 × -343, ΔH.sub.r.sup.0 (298 K.) =                              -545 kJ mol.sup.-1                                      and                                                                            [II-768]                                                                             0.5 Rh.sub.2 O.sub.3 (cr) + 0.5 O(g) → RhO.sub.2 (g)              0.5 × -343                                                                           0.5 × 249                                                                           +184, ΔH.sub.r.sup.0 (298 K.) =                                          +231 kJ mol.sup.-1.                                     ______________________________________                                    

Thus, the sesquioxide is the product of the reaction of monoxygen with rhodium.

    __________________________________________________________________________     [II-769]                                                                           RhCl.sub.3 (cr) + 7.5 O(g) → 0.5 Rh.sub.2 O.sub.3 (cr) + 3              ClO.sub.2 (g)                                                              -299    7.5 × 249                                                                      0.5 × -343                                                                      3 × 102, ΔH.sub.r.sup.0 (298 K.) = -1434                           kJ mol.sup.-1,                                            __________________________________________________________________________

and monoxygen will also convert the trichloride to the sesquioxide.

    __________________________________________________________________________     [II-770]                                                                           4 Rh(cr) + 12 CO(g) → Rh.sub.4 (CO).sub.12 (cr)                     0     12 × -110                                                                      -1825, ΔH.sub.r.sup.0 (298 K.) = -505 kJ mol.sup.-1,         [II-771]                                                                           2 Rh.sub.2 O.sub.3 (cr) + 18 CO(g) → Rh.sub.4 (CO).sub.12 (cr)          + 6 CO.sub.2 (g)                                                           2 × -343                                                                           18 × -110                                                                      -1825                                                                              6 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1523 kJ                                       mol.sup.-1,                                          [II-772]                                                                           4 RhCl.sub.3 (cr) + 24 CO(g) → Rh.sub.4 (CO).sub.12 (cr) + 6            COCl(g)                                                                    4 × -299                                                                           24 × -110                                                                      -1825                                                                              6 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +1633 kJ                                       mol.sup.-1,                                          and                                                                            [II-773]                                                                           4 RhCl.sub.3 (cr) + 24 CO*(g) → Rh.sub.4 (CO).sub.12 (cr) + 6           COCl(g)                                                                     4 × -299                                                                          24 × 564                                                                       -1825                                                                              6 × -63,                                                                       ΔH.sub.r *(298 K.) = -14,543 kJ                                          mol.sup.-1.                                          __________________________________________________________________________

Since reaction [II-771] is expected to be slow with ground state carbon monoxide, but fast with the excited state carbon monoxide, only the excited state carbon monoxide is recommended. (The reason that the slow rate is expected is that in the carbonyl compound the rhodium atoms form a tetrahedron, whereas in the sesquioxide each rhodium is surrounded octahedrally by oxygens. The energentics of the excited state carbon monoxide is so great that the rhodium atoms will be quite mobile when the oxygens separating them are removed in the formation of carbon dioxide.) The recommended procedures, thus, are:

O+CO*

CO*.

8. PALLADIUM

The paucity of thermodynamic data on the palladium species precludes an extensive analysis at this time.

    __________________________________________________________________________     [II-774]                                                                           Pd(cr) + O(g) → PdO(cr)                                             0      249                                                                               -85,                                                                               ΔH.sub.r.sup.0 (298 K.) = -334 kJ mol.sup.-1,              [II-775]                                                                           PdCl.sub.2 (cr) + 5 O(g) → PdO(cr) + 2 ClO.sub.2 (g)                -199   5 × 249                                                                       -85 2 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -927 kJ mol.sup.-1       and                                                                            [II-776]                                                                           PdF.sub.2 (cr) + 5 O(g) → PdO(cr) + 2 FO.sub.2 (g)                  -469   5 × 249                                                                       -85 2 × 13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -835 kJ                                        mol.sup.-1.                                              [II-777]                                                                           Pd(cr) + 2 F(g) → PdF.sub.2 (cr)                                    0      2 × 79                                                                      -469,                                                                              ΔH.sub.r.sup.0 (298 K.) = -627 kJ mol.sup.-1,              [II-778]                                                                           PdO(cr) + 4 F(g) → PdF.sub.2 (cr) + 2 OF.sub.2 (g)                  -85    4 × 79                                                                        -469                                                                               2 × -24,                                                                       ΔH.sub.r.sup.0 (298 K.) = -652 kJ mol.sup.-1       and                                                                            [II-779]                                                                           PdCl.sub.2 (cr) + 8 F(g) → PdF.sub.2 (cr) + 2 ClF.sub.3 (g)         -199   8 × 79                                                                        -469                                                                               2 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1220 kJ                 __________________________________________________________________________                           mol.sup.-1.                                         

The vapor pressures of Pd(acac)₂ and Pt(acac)² are 1 mm at 74°-94° C. and 80°-102° C., respectively <II-35>. Furthermore, Pt (hfa)₂ sublimes at 65° C., <II-36>. Thus, hfa is expected to be an effective volatilizing reagent for palladium. The question, however, must be asked whether hfa is an effective volatilizing reagent for palladium species other than the metal itself? Will, for example,

    ______________________________________                                         [II-780]                                                                             PdF.sub.2 (cr) + 4 hfa(g) → Pd(hfa).sub.2 (g) + 2 F(hfa)(g)       occur?                                                                               Consider the reactions                                                   [II-781]                                                                             CHF(g) → CH(g) + F(g)                                             126       594    79,    ΔH.sub.r.sup.0 (298 K.) = +547 kJ                                        mol.sup.-1,                                            [II-782]                                                                             CHF(g) → CF(g) + H(g)                                             126       255    218,   ΔH.sub.r.sup.0 (298 K.) = +347 kJ                                        mol.sup.-1,                                            [II-783]                                                                             CF(g) → C(g) + F(g)                                               255       717    79,    ΔH.sub.r.sup.0 (298 K.) = +541 kJ                                        mol.sup.-1                                             and                                                                            [II-784]                                                                             CH(g) → C(g) + H(g)                                               594       717    218,   ΔH.sub.r.sup.0 (298 K.) = +341 kJ                                        mol.sup.-1.                                            ______________________________________                                    

Thus, we see that the C-F, bond strength is of the order of 540-550 kJ mol⁻¹, whereas the C-H bond strength is only of the order of 340-350 kJ mol⁻¹. The compound F(hfa) is, therefore, a stabile compound.

There would appear to be a contradiction here since we assumed a ΔH_(r) of 418 kJ mol⁻¹ for [II-682]. There actually is no contradiction since H-βdik(g) is the enol. The hydrogen is bonded to oxygen!

    ______________________________________                                         [II-785]                                                                             OH(g) → O(g) + H(g)                                               39        249    218, ΔH.sub.r.sup.0 (298 K.) = +428 kJ mol.sup.-                         1,                                                            and                                                                            [II-786]                                                                             CH.sub.3 OH(g) → CH.sub.3 O(g) → H(g)                      -201      18     218, ΔH.sub.r.sup.0 (298 K.) = +437 kJ                  ______________________________________                                                          mol.sup.-1,                                              

(The datum for methanol is from Ref. <B>, and the datum for methoxy is from Ref. <II-13>.) The value for H-βdik(g) is somewhat lower because of the reasonance stabilization of βdik.

9. OSMIUM

    __________________________________________________________________________     [II-787]                                                                           Os(cr) + 3 O(g) → OsO.sub.3 (g)                                     0     3 × 249                                                                        -284,                                                                              ΔH.sub.r.sup.0 (298 K.) = -1031 kJ mol.sup.-1,           [II-788]                                                                           Os(cr) + 4 O(g) → OsO.sub.4 (cr)                                    0     4 × 249                                                                        -394,                                                                              ΔH.sub.r.sup.0 (298 K.) = -1390 kJ mol.sup.-1            0     4 × 232                                                                        -305,                                                                              ΔG.sub.r.sup.0 (298 K.) = -1233 kJ mol.sup.-1,           [II-789]                                                                           OsCl.sub.3 (cr) + 10 O(g) → OsO.sub.4 (cr) + 3 ClO.sub.2 (g)        -190      10 × 249                                                                       -394                                                                               3 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2388 kJ                                       mol.sup.-1                                           and                                                                            [II-790]                                                                           OsCl.sub.4 (cr) + 12 O(g) → OsO.sub.4 (cr) + 4 ClO.sub.2 (g)        -255      12 × 249                                                                       -394                                                                               4 ×  102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2719 kJ                                       mol.sup.-1.                                          [II-791]                                                                           3 Os(cr) + 12 CO(g) → Os.sub.3 (CO).sub.12 (cr)                     0     12 × -110                                                                      -1749,                                                                             ΔH.sub.r.sup.0 (298 K.) = -429 kJ mol.sup.-1,            [II-792]                                                                           3 OsCl.sub.3 (cr) + 21 CO(g) → Os.sub.3 (CO).sub.12 (cr) + 9            COCl(g)                                                                    3 × -190                                                                           21 × -110                                                                      -1749                                                                              9 × -63,                                                                       ΔH.sub.r.sup.0 (298 K.) = +564 kJ                                        mol.sup.-1,                                          [II-793]                                                                           3 OsCl.sub.3 (cr) + 21 CO*(g) → Os.sub.3 (CO).sub.12 (cr) + 9           COCl(g)                                                                    3 × -190                                                                           21 × 564                                                                       -1749                                                                              9 × -63,                                                                       ΔH.sub.r *(298 K.) = -13,590 kJ                                          mol.sup.-1,                                          [II-794]                                                                           3 OsCl.sub.4 (cr) + 24 CO(g) → Os.sub.3 (CO).sub. 12 (cr) + 12          COCl(g)                                                                    3 × -255                                                                           24 × -110                                                                      -1749                                                                              12 × -63,                                                                      ΔH.sub.r.sup.0 (298 K.) = +900 kJ                                        mol.sup.-1                                           and                                                                            [II-795]                                                                           3 OsCl.sub.4 (cr) + 24 CO*(g) → Os.sub.3 (CO).sub.12 (cr) + 12          COCl(g)                                                                    3 × -255                                                                           24 × 564                                                                       -1749                                                                              12 × -63,                                                                      ΔH.sub.r *(298 K.) = -15,276 kJ                                          mol.sup.-1.                                          __________________________________________________________________________

Thus, there are two choices of procedures for the volatilization of osmium species:

CO*.

The monoxygen procedure is usually the preferred procedure.

10. IRIDIUM

    ______________________________________                                         [II-796]                                                                             Ir(cr) + 2 O(g) → IrO.sub.2 (cr)                                  0         2 × 249                                                                           -274, ΔH.sub.r.sup.0 (298 K.) =                                          -772 kJ mol.sup.-1,                                         [II-797]                                                                             IrO.sub.2 (cr) + O(g) → IrO.sub.3 (g)                             -274      249      8, ΔH.sub.r.sup.0 (298 K.) =                                             +33 kJ mol.sup.-1,                                          [II-798]                                                                             IrCl(cr) + 4 O(g) → IrO.sub.2 (cr) + ClO.sub.2 (g)                -82       4 × 249                                                                           -274     102, ΔH.sub.r.sup.0 (298 K.) =                                           -1086 kJ mol.sup.-1                                and                                                                            [II-799]                                                                             IrCl.sub.3 (cr) + 8 O(g) → IrO.sub.2 (cr) + 3 ClO.sub.2 (g)       -246      8 × 249                                                                           -274     3 × 102, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -1714 kJ mol.sup.-1.                               ______________________________________                                    

If O* were used in [II-797] rather than O, the enthalpy of reaction would be -247 kJ mol⁻¹. Since we know very little about the trioxide at the present time, we cannot recommend O* as a volatilizing procedure.

    __________________________________________________________________________     [II-800]                                                                           Ir(cr) + 6 F(g) → IrF.sub.6 (cr)                                    0     6 × 79                                                                         -580,                                                                              ΔH.sub.r.sup.0 (298 K.) = -1054 kJ mol.sup.-1            0     6 × 62                                                                         -462,                                                                              ΔH.sub.r.sup.0 (298 K.) = -834 kJ mol.sup.-1,            [II-801]                                                                           IrO.sub.2 (cr) + 10 F(g) → IrF.sub.6 (cr) + 2 OF.sub.2 (g)          -274      10 × 79                                                                        -580                                                                               2 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1048 kJ                                       mol.sup.-1,                                          [II-802]                                                                           IrCl(cr) + 9 F(g) → IrF.sub.6 (cr) + ClF.sub.3 (g)                  -82       9 × 79                                                                         -580                                                                               -159, ΔH.sub.r.sup.0 (298 K.) = -1368 kJ                                       mol.sup.-1                                           and                                                                            [II-803]                                                                           IrCl.sub.3 (cr) + 15 F(g) → IrF.sub.6 (cr) + 3 ClF.sub.3 (g)        -246      15 ×  79                                                                       -580                                                                               3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1996 kJ                                       mol.sup.-1.                                          [II-804]                                                                           4 Ir(cr) + 12 CO(g) → Ir.sub.4 (CO).sub.12 (cr)                     0     12 × -110                                                                      -1820,                                                                             ΔH.sub.r.sup.0 (298 K.) = -500 kJ mol.sup.-1,            [II-805]                                                                           4 IrO.sub.2 (cr) + 20 CO(g) → Ir.sub.4 (CO).sub.12 (cr) + 8             CO.sub.2 (g)                                                               4 × -274                                                                           20 × -110                                                                      -1820                                                                              8 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1676 kJ                                       mol.sup.-1                                           [II-806]                                                                           4 IrCl(cr) + 16 CO(g) → Ir.sub.4 (CO).sub.12 (cr) + 4 COCl(g)       4 × -82                                                                            16 × -110                                                                      -1820                                                                              4 × -394,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1308 kJ                                       mol.sup.-1                                           and                                                                            [II-807]                                                                           4 IrCl.sub.3 (cr) + 24 CO(g) → Ir.sub.4 (CO).sub.12 (cr) + 12           COCl(g)                                                                    4 × -246                                                                           24 × -110                                                                      -1820                                                                              12 × -394,                                                                     ΔH.sub.r.sup.0 (298 K.) = -2924 kJ                                       mol.sup.-1.                                          __________________________________________________________________________

The possible procedures for the volatilization of iridium species are:

O* (?)

O+F

O+CO

CO.

11. PLATINUM

    __________________________________________________________________________     [II-808]                                                                           3 Pt(cr) + 4 O(g) → Pt.sub.3 O.sub.4 (cr)                           0       4 × 249                                                                       -163,                                                                               ΔH.sub.r.sup.0 (298 K.) = -1159 kJ mol.sup.-1,         [II-809]                                                                           Pt.sub.3 O.sub.4 (cr) + 2 O(g) → 3 PrO.sub.2 (g)                    -163    2 × 249                                                                       3 × 172,                                                                      ΔH.sub.r.sup.0 (298 K.) = +181 kJ mol.sup.-1,          [II-810]                                                                           3 PtCl(cr) + 10 O(g) → Pt.sub.3 O.sub.4 (cr) + 3 ClO.sub.2              (g)                                                                        3 × -56                                                                            10 × 249                                                                      -163  3 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -2179 kJ                                       mol.sup.-1,                                         [II-811]                                                                           3 PtCl.sub.2 (cr) + 16 O(g) → Pt.sub.3 O.sub.4 (cr) + 6                 ClO.sub.2 (g)                                                              3 × -123                                                                           16 × 249                                                                      -163  6 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -3166 kJ                                       mol.sup.-1,                                         [II-812]                                                                           3 PtCl.sub.3 (cr) + 22 O(g) → Pt.sub.3 O.sub.4 (cr) + 9                 ClO.sub.2 (g)                                                              3 × -182                                                                           22 × 249                                                                      -163  9 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -4177 kJ                                       mol.sup.-1,                                         [II-813]                                                                           3 PtCl.sub.4 (cr) + 28 O(g) → Pt.sub.3 O.sub.4 (cr) + 12                ClO.sub.2 (g)                                                              3 × -232                                                                           28 × 249                                                                      -163  12 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -5215 kJ                                       mol.sup.-1,                                         [II-814]                                                                           3 PtF.sub.4 (cr) + 28 O(g) → Pt.sub.3 O.sub.4 (cr) + 12                 FO.sub.2 (g)                                                               3 × -681                                                                           28 × 249                                                                      -163  12 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -4936 kJ                                       mol.sup.-1,                                          [II-815]                                                                          3 PtF.sub.6 (cr) + 40 O(g) → Pt.sub.3 O.sub.4 (cr) + 18                 FO.sub.2 (g)                                                               3 × -722                                                                           40 × 249                                                                      -163  18 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -7723 kJ                                       mol.sup.-1,                                         [II-816]                                                                           Pt(cr) + 4F(g) → PtF.sub.4 (cr)                                     0       4 × 79                                                                        -681,                                                                               ΔH.sub.r.sup.0 (298 K.) = -997 kJ mol.sup.-1,          [II-817]                                                                           Pt.sub.3 O.sub.4 (cr) + 20 F(g) → 3 PtF.sub.4 (cr) + 4                  OF.sub.2 (g)                                                               -163      20 × 79                                                                       3 × -681                                                                       4 × 24,                                                                        ΔH.sub.r.sup.0 (298 K.) = -3364 kJ                                       mol.sup.-1,                                         [II-818]                                                                           PtCl(cr) + 7 F(g) → PtF.sub.4 (cr) + ClF.sub.3 (g)                  -56       7 × 79                                                                        -681  -159, ΔH.sub.r.sup.0 (298 K.) = -1337 kJ                                       mol.sup.-1,                                         [II-819]                                                                           PtCl.sub.2 (cr) + 10 F(g) → PtF.sub.4 (cr) + 2 ClF.sub.3 (g)        -123      10 × 79                                                                       -681  2 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -1666 kJ                                       mol.sup.-1,                                         [II-820]                                                                           PtCl.sub.3 (cr) + 13 F(g) → PtF.sub.4 (cr) + 3 ClF.sub.3 (g)        -182      13 × 79                                                                       -681  3 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2003 kJ                                       mol.sup.-1,                                         [II-821]                                                                           PtCl.sub.4 (cr) + 16 F(g) → PtF.sub.4 (cr) + 4 ClF.sub.3 (g)        -232      16 × 79                                                                       -681  4 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) = -2349 kJ                                       mol.sup.-1                                          and                                                                            [II-822]                                                                           PtF.sub.4 (cr) + 2 F(g) → PtF.sub.6 (cr)                            -681    2 × 79                                                                        -722,                                                                               ΔH.sub.r.sup.0 (298 K.) = -199 kJ                      __________________________________________________________________________                       mol.sup.-1.                                             

The possible procedures for the volatilization of platinum species are:

O+F

F (in the absence of PtF₆).

P. Group IB.

1. THERMODYNAMICS

Of the various species listed in TABLE II-21. only three have significantly low `times four` criteria:

    ______________________________________                                         Cu.sub.2 O    cr → l                                                                              236 kJ mol.sup.-1                                    CuF.sub.2     cr → l                                                                              204                                                                cr → g                                                                             1088                                                  AuCl.sub.3    cr → g                                                                              278.                                                 ______________________________________                                    

In addition we should note the discussion of Cu(hfa)₂ in SECTION IX.O.2. have no volatile silver species to consider.

                  TABLE II-21                                                      ______________________________________                                         GROUP I B                                                                      THERMODYNAMIC DATA                                                             ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.f.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES  Cu          Ag           Au                                           ______________________________________                                          M.sub.2 O                                                                           (cr)   -171/-148   -31a/-11a                                                   (l)    -112/-100                                                         MO    (cr)   -156/-128                                                         M.sub.2 O.sub.2                                                                      (cr)                -24a/+28a                                                  (g)    +306/+277                                                         M.sub.2 O.sub.3                                                                      (cr)                +34a/+121a                                                                                -3b/--                                    MCl   (cr)   -138/-121   -127a/-110a                                                                                -35a/--                                         (l)    -131/-116                                                               (g)     +91/+64               +197a/--                                   MCl.sub.2                                                                            (cr)   -206/-162                                                         MCl.sub.3                                                                            (cr)                          -118a/--                                   M.sub.2 Cl.sub.6                                                                     (g)                            -97a/--                                   MF    (cr)   -280/-260   -205a/--                                                    (g)     -13/-40                -75b/--                                   MF.sub.2                                                                             (cr)   -539/-492   -360a/--   -238b/--                                         (l)    -488/-454                                                               (g)    -267/-276                                                         MF.sub.3                                                                             (cr)                          -364a/--                                   ______________________________________                                          (a, Ref. <B>; b, Ref. <II23>)                                            

    ______________________________________                                         [ II-823]                                                                               2 Cu(cr) + O(g) → Cu.sub.2 O(cr)                                      0      249      -171, ΔH.sub.r.sup.0 (298 K.) =                                          -420 kJ mol.sup.-1                                             0      232      -148, ΔG.sub.r.sup.0 (298 K.) =                                          -380 kJ mol.sup.-1,                                     and                                                                            [II-824] Cu.sub.2 O(cr) + O(g) → 2 CuO(cr)                                     -171   249      2 × -156, ΔH.sub.r.sup.0 (298 K.) =                                -390 kJ mol.sup.-1                                             -148   232      2 × -128, ΔG.sub.r.sup.0 (298 K.) =                                -340 kJ mol.sup.-1.                                     ______________________________________                                    

Cuprous oxide will be formed in the liquid state. It will react further with monoxygen to form cupric oxide. The cupric oxide will not volatilize.

    __________________________________________________________________________     [II-825]                                                                           CuCl(cr) + 3 O(g) → CuO(cr) + ClO.sub.2 (g)                         -138    3 × 249                                                                       -156  102,  ΔH.sub.r.sup.0 (298 K.) = -663 kJ                                        mol.sup.-1                                            -121    3 × 232                                                                       -128  120,  ΔG.sub.r.sup.0 (298 K.) = -583 kJ                                        mol.sup.-1,                                           [II-826]                                                                           CuCl.sub.2 (cr) + 5 O(g) → CuO(cr) + 2 ClO.sub.2 (g)                -206    5 × 249                                                                       -156  2 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -991 kJ                                        mol.sup.-1                                            -162    5 × 232                                                                       -128  2 × 120,                                                                       ΔG.sub.r.sup.0 (298 K.) = -886 kJ                                        mol.sup.-1,                                           [II-827]                                                                           CuF(cr) + 3 O(g) → CuO + FO.sub.2 (g)                               -280    3 × 249                                                                       -156  13,   ΔH.sub.r.sup.0 (298 K.) = -610 kJ                                        mol.sup.-1                                            -260    3 × 232                                                                       -128  27,   ΔG.sub.r.sup.0 (298 K.) = -537 kJ                                        mol.sup.-1                                            and                                                                            [II-828]                                                                           CuF.sub.2 (cr) + 5 O(g) → CuO(cr) + 2 FO.sub.2 (g)                  -539    5 × 249                                                                       -156  2 × 13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -836 kJ                                        mol.sup.-1                                            -492    5 × 232                                                                       -128  2 × 27,                                                                        ΔG.sub.r.sup.0 (298 K.) = -742 kJ                                        mol.sup.-1.                                           [II-829]                                                                           Cu(cr) + F(g) → CuF(cr)                                             0      79                                                                               -280,                                                                              ΔH.sub.r.sup.0 (298 K.) = -359 kJ mol.sup.-1                0      62                                                                               -260,                                                                              ΔG.sub.r.sup.0 (298 K.) = -322 kJ mol.sup.-1,               [II-830]                                                                           CuF(cr) + F(g) → CuF.sub.2 (cr)                                     -280   79                                                                               -539,                                                                              ΔH.sub.r.sup.0 (298 K.) = -338 kJ mol.sup.-1                -260   62                                                                               -492,                                                                              ΔG.sub.r.sup.0 (298 K.) = -294 kJ mol.sup.-1,               [II-831]                                                                           Cu.sub.2 O(cr) + 6 F(g) → 2 CuF.sub.2 (cr) + OF.sub.2 (g)           -171    6 × 79                                                                        2 × -539                                                                       24,   ΔH.sub.r.sup.0 (298 K.) = -1357 kJ                                       mol.sup.-1                                            -148    6 × 62                                                                        2 × -492                                                                       43,   ΔG.sub.r.sup.0 (298 K.) = -1166 kJ                                       mol.sup.-1,                                           [II-832]                                                                           Cu.sub.2 O(cr) + 6 F*(g) → 2 CuF.sub.2 (cr) + OF.sub.2 (g)          -171    6 × 245                                                                       2 × -539                                                                       24,   ΔH.sub.r *(298 K.) = -2353 kJ mol.sup.-1,       [II-833]                                                                           CuO(cr) + 4 F(g) → CuF.sub.2 (cr) + OF.sub.2 (g)                    -138    4 × 79                                                                        -539  24,   ΔH.sub.r.sup.0 (298 K.) = -693 kJ mol.sup.                               -1                                                    -11     4 × 62                                                                        -492  42,   ΔG.sub.r.sup.0 (298 K.) = -577 kJ                                        mol.sup.-1,                                           [II-834]                                                                           CuO(cr) + 4 F*(g) → CuF.sub.2 (cr) + OF.sub.2 (g)                   -138    4 × 245                                                                       -539  24,   ΔH.sub.r.sup.0 (298 K.) = -1357 kJ                                       mol.sup.-1,                                           [II-835]                                                                           CuCl(cr) + 5 F(g) → CuF.sub.2 (cr) + ClF.sub.3 (g)                  -138    5 × 79                                                                        -539  -159, ΔH.sub.r.sup.0 (298 K.) = -955 kJ                                        mol.sup.-1                                            -121    5 × 62                                                                        -492  -119, ΔG.sub.r.sup.0 (298 K.) = -800 kJ                                        mol.sup.-1                                            and                                                                            [II-836]                                                                           CuCl.sub.2 (cr) + 8 F(g) → CuF.sub.2 (cr) + 2 ClF.sub.3 (g)         -206    8 × 79                                                                        -539  2 × -159,                                                                      ΔH.sub.r.sup.0 (298 K.) =  -1283 kJ                                      mol.sup.-1                                            -162    8 × 62                                                                        -492  2 × -119,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1064 kJ                                       mol.sup.-1.                                           __________________________________________________________________________

Thus, we have the choice of two procedures for the volatilization of copper species:

O+F*

F+hfa.

3. SILVER

    ______________________________________                                         [II-837]                                                                             2 Ag(cr) + O(g) → Ag.sub.2 O(cr)                                  0         249     -31, ΔH.sub.r.sup.0 (298 K.) = -280 kJ                                   mol.sup.-1,                                                  0         232     -11, ΔG.sub.r.sup.0 (298 K.) = -243 kJ                                   mol.sup.-1,                                                  [II-838]                                                                             Ag.sub.2 O(cr) + O(g) → Ag.sub.2 O.sub.2 (cr)                     -31       249     -24, ΔH.sub.r.sup.0 (298 K.) = -242 kJ                                   mol.sup.-1                                                   -11       232     +28, ΔG.sub.r.sup.0 (298 K.) = -193 kJ                                   mol.sup.-1                                                   and                                                                            [II-839]                                                                             Ag.sub.2 O.sub.2 (cr) + O(g) → Ag.sub.2 O.sub.3 (cr)              -24       249      34, ΔH.sub.r.sup.0 (298 K.) = -191 kJ                                   mol.sup.-1                                                   28        232     121, ΔG.sub.r.sup.0 (298 K.) = -139 kJ                 ______________________________________                                                           mol.sup.-1.                                             

Thus, although dioxygen will take silver only to the argentous oxide, monoxygen will take it all the way to the sesquioxide.

    __________________________________________________________________________     [II-840]                                                                           2 AgCl(cr) + 7 O(g) → Ag.sub.2 O.sub.3 (cr) + 2 ClO.sub.2 (g)       2 × -127                                                                           7 × 249                                                                       34    2 × 102                                                                       ΔH.sub.r.sup.0 (298 K.) = -1251 kJ                                       mol.sup.-1                                           2 × -110                                                                           7 × 232                                                                       121   2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -1043 kJ                                       mol.sup.-1,                                          [II-841]                                                                           2 AgF(cr) + 7 O(g) → Ag.sub.2 O.sub.3 (cr) + 2 FO.sub.2 (g)         2 × -205                                                                           7 × 249                                                                       34    2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1273 kJ                                       mol.sup.-1                                           and                                                                            [II-842]                                                                           2 AgF.sub.2 (cr) + 11 O(g) → Ag.sub.2 O.sub.3 (cr) + 4                  FO.sub.2 (g)                                                               2 × -360                                                                           11 × 249                                                                      34    4 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) =  -1933 kJ                                      mol.sup.-1.                                          [II-843]                                                                           Ag(cr) + F(g) → AgF(cr)                                             0       79                                                                               -205, ΔH.sub.r.sup.0 (298 K.) = -284 kJ mol.sup.-1,            [II-844]                                                                           AgF(cr) + F(g) → AgF.sub.2 (cr)                                     -205    79                                                                               -360, ΔH.sub.r.sup.0 (298 K.) = -234 kJ mol.sup.-1,            [II-845]                                                                           Ag.sub.2 O(cr) + 4 F(g) → 2 AgF(cr) + OF.sub.2 (g)                  -31       4 × 79                                                                        2 × -205                                                                       13,  ΔH.sub.r.sup.0 (298 K.) = -682 kJ                                        mol.sup.-1,                                          [II-846]                                                                           Ag.sub.2 O.sub.2 (cr) + 6 F(g) → 2 AgF(cr) + 2 OF.sub.2 (g)         -24       6 × 79                                                                        2 × -205                                                                       2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -834 kJ                                        mol.sup.-1,                                          [II-847]                                                                           Ag.sub.2 O.sub.3 (cr) + 8 F(g) → 2 AgF(cr) + 3 OF.sub.2 (g)         34        8 × 79                                                                        2 × -205                                                                       3 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -1037 kJ                                       mol.sup.-1                                           and                                                                            [II-848]                                                                           AgCl(cr) + 4 F(g) → AgF(cr) + ClF.sub.3 (g)                         -127      4 × 79                                                                        -205  -159,                                                                               ΔH.sub.r.sup.0 (298 K.) = -553 kJ                                        mol.sup.-1.                                          __________________________________________________________________________

In the absence of data on volatile silver species we can make no recommendations at this time.

4. GOLD

Gold trichloride sublimes at 180° at 760 nm <II-37>. At the time that SECTION V. was written we had not considered monochlorine as a potential volatilizing reagent. A discussion of it was therefore, not included. It should be noted that, whereas the datum for crystalline gold trichloride is for the monomer the datum for gaseous gold trichloride is for the dimer.

    __________________________________________________________________________     [II-849]                                                                           2 Au(cr) + 3 O(g) → Au.sub.2 O.sub.3 (cr)                           0       3 × 249                                                                       -3, ΔH.sub.r.sup.0 (298 K.) = -750 kJ mol.sup.-1,           [II-850]                                                                           2 AuCL(cr) + 7 O(g) → Au.sub.2 O.sub.3 (cr) + 2 ClO.sub.2 (g)       2 × -35                                                                            7 × 249                                                                       -3,   2 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = - 1472 kJ                                      mol.sup.-1,                                         [II-851]                                                                           2 AuCl.sub.3 (cr) + 15 O(g) → Au.sub.2 O.sub.3 (cr) + 6                 ClO.sub.2 (g)                                                              2 × -35                                                                            15 × 249                                                                      -3    6 × 102,                                                                       ΔH.sub.r.sup.0 (298 K.) = -3056 kJ                                       mol.sup.-1,                                         [II-852]                                                                           2 AuF.sub.2 (cr) + 11 O(g) → Au.sub.2 O.sub.3 (cr) + 4                  FO.sub.2 (g)                                                               2 × -238                                                                           11 × 249                                                                      -3    4 × 13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -2214 kJ                                       mol.sup.-1                                          and                                                                            [II-853]                                                                           2 AuF.sub.3 (cr) + 15 O(g) → Au.sub.2 O.sub.3 (cr) + 6                  FO.sub.2 (g)                                                               2 × -364                                                                           15 × 249                                                                      -3    6 × 13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -2932 kJ                                       mol.sup.-1.                                         [II-854]                                                                           Au(cr) + F(g) → AuF(g)                                              0       79   -75,                                                                               ΔH.sub.r.sup.0 (298 K.) = -154 kJ mol.sup.-1,           [II-855]                                                                           Au(cr) + 2 F(g) → AuF.sub.2 (cr)                                    0       2 × 79                                                                        -238,                                                                              ΔH.sub.r.sup.0 (298 K.) = -396 kJ mol.sup.-1,           [II-856]                                                                           AuF.sub.2 (cr) + F(g) → AuF.sub.3 (cr)                              -238    79   -364,                                                                              ΔH.sub.r.sup.0 (298 K.) =  -205 kJ mol.sup.-1,          [II-857]                                                                           Au.sub.2 O.sub.3 (cr) + 10 F(g) → 2 AuF.sub.2 (cr) + 3                  OF.sub.2 (g)                                                               -3        10 × 79                                                                       2 × -238                                                                       3 × 13,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1224 kJ                                       mol.sup.-1,                                         [II-858]                                                                           AuCl(cr) + 3 F(g) → AuF.sub.2 (cr) + ClF(g)                         -35       3 × 79                                                                        -238  -50,  ΔH.sub.r.sup.0 (298 K.) = -490 kJ                                        mol.sup.-1                                          and                                                                            [II-859]                                                                           AuCl.sub.3 (cr) + 5 F(g) → AuF.sub.2 (cr) + 3 ClF(g)                -118      5 × 79                                                                        -238  3 × -50,                                                                       ΔH.sub.r.sup.0 (298 K.) = -665 kJ                                        mol.sup.-1,                                         [II-860]                                                                           Au(cr) + 3 Cl(g) + AuCl.sub.3 (cr)                                         0       3 × 121                                                                       -118,                                                                              ΔH.sub. r.sup.0 (298 K.) = -481 kJ mol.sup.-1,          [II-861]                                                                           Au.sub.2 O.sub.3 (cr) + 9 Cl(g) → 2 AuCl.sub.3 (cr) + 3                 OCl.sub.2 (g)                                                              -3        9 × 121                                                                       2 × -118                                                                       3 × 88,                                                                        ΔH.sub.r.sup.0 (298 K.) = -1058 kJ                                       mol.sup.-1,                                         [II-862]                                                                           AuCl(cr) + 2 Cl(g) → AuCl.sub.3 (cr)                                -35     2 × 121                                                                       -118,                                                                              ΔH.sub.r.sup.0 (298 K.) = -325 kJ mol.sup.-1,           [II-863]                                                                           AuF.sub.2 (cr) + 5 Cl(g) → AuCl.sub.3 (cr) + 2 ClF(g)               -238      5 × 121                                                                       -118  2 × -50,                                                                       ΔH.sub.r.sup.0 (298 K.) = -585 kJ                                        mol.sup.-1                                          and                                                                            [II-864]                                                                           AuF.sub.3 (cr) + 6 Cl(g) → AuCl.sub.3 (cr) + 3 ClF(g)               -364      6 × 121                                                                       -118  3 × -50,                                                                       ΔH.sub.r.sup.0 (298 K.) = -630 kJ                                        mol.sup.-1.                                         __________________________________________________________________________

Thus, we have the choice of four procedures for the volatilization of gold species:

O+F+Cl

O+Cl

F+Cl

Q. Group IIB

1. THERMODYNAMICS

                  TABLE II-22                                                      ______________________________________                                         THERMODYNAMIC DATA                                                             GROUP IIB.                                                                     ΔH.sub.f.sup.0 (298 K.)/ΔG.sub.r.sup.0 (298 K.)                    (kJ mol.sup.-1)                                                                SPECIES  Zn          Cd          Hg                                            ______________________________________                                         MO                                                                             (cr)     -348a/-318a -258a/-228   -91/-58                                      (g)                               +42/+23                                      M.sub.2 Cl.sub.2                  -265/-210                                    (cr)                                                                           MCl                               +78/+57                                      (g)                                                                            MCl.sub.2                                                                      (cr)     -415a/-369a -392a/-344a  -230/-184                                    (l)                               -213/-173                                    (g)      -266a/--                 -146/-145                                    M.sub.2 F.sub.2                   -485/-469                                    (cr)                                                                           MF                                 +3/-18                                      (g)                                                                            MF.sub.2                                                                       (cr)     -764a/-713a -700a/-648a  -423/-374                                    (l)      -735b/--    -677b/--     -405/-362                                    (g)      -551b/--    -459b/--     -294/-292                                    (CH.sub.3)M                      +167a/--                                      (g) -(CH.sub.3).sub.2 M                                                        (l)       +23a/--     +64a/+139a  +60a/+140a                                   (g)       +53a/--    + 102a/+147a                                                                                +94a/+146a                                   ______________________________________                                          (a., Ref. <B>; b., Ref. <II23>)                                          

By the criterion of [II-1] the dimethyl compounds of cadmium and mercury will volatilize spontaneously in the Apparatus. The `times four` criterion for some species of interest are

    ______________________________________                                         ZnF.sub.2      cr    → l                                                                              116 kJ mol.sup.-1                                               cr    → g                                                                              852                                              (CH.sub.3).sub.2 Zn                                                                           l     → g                                                                              120                                              CdF.sub.2)     cr    → l                                                                               92                                                             cr    → g                                                                              964                                              HgO            cr    → g                                                                              532                                              HgF            cr    → g                                                                              982 (monomer)                                    HgF.sub.2      cr    → l                                                                               72                                                             cr    → g                                                                              516.                                             ______________________________________                                    

It should be noted that mercurous fluoride is a dimer in the crystalline state and a monomer in the gaseous state.

2. ZINC

    ______________________________________                                         [II-865]                                                                             Zn(cr) + O(g) → ZnO(cr)                                           0         249      -348, ΔH.sub.r.sup.0 (298 K.) =                                          -597 kJ mol.sup.-1                                          0         232      -318, ΔG.sub.r.sup.0 (298 K.) =                                          -550 kJ mol.sup.-1,                                         [II-866]                                                                             ZnCl.sub.2 (cr) + 5 O(g) → ZnO(cr) + 2 ClO.sub.2 (g)              -415      5 × 249                                                                           -348    2 × 102, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -974 kJ mol.sup.-1                                  -369      5 × 232                                                                           -318    2 × 120, ΔG.sub.r.sup.0 (298 K.)                                   =                                                                              -869 kJ mol.sup.-1                                  and                                                                            [II-867]                                                                             ZnF.sub.2 (cr) + 5 O(g) → ZnO(cr) + 2 FO.sub.2 (g)                -764      5 × 249                                                                           -348    2 × 13, ΔH.sub.r.sup.0 (298 K.) =                                  -803 kJ mol.sup.-1                                  -713      5 × 232                                                                           -318    2 × 27, ΔG.sub.r.sup.0 (298 K.) =                                  -711 kJ mol.sup.-1,                                 [II-868]                                                                             Zn(cr) + 2 F(g) → ZnF.sub.2 (cr)                                  0         2 × 79                                                                            -764, ΔH.sub.r.sup.0 (298 K.) =                                          -922 kJ mol.sup.-1,                                         0         2 × 62                                                                            -713, ΔG.sub.r.sup.0 (298 K.) =                                          -837 kJ mol.sup.-1,                                         [II-869]                                                                             ZnO(cr) + 4 F(g) → ZnF.sub.2 (cr) + OF.sub.2 (g)                  -348      4 × 79                                                                            -764    24, ΔH.sub.r.sup.0 (298 K.) =                                            -708 kJ mol.sup.-1,                                 -318      4 × 62                                                                            -713,   42, ΔG.sub.r.sup.0 (298 K.) =                                            -601 kJ mol.sup.-1,                                 [II-870]                                                                             ZnO(cr) + 4 F*(g) → ZnF.sub.2 (cr) + OF.sub.2 (g)                 -348      4 × 245                                                                           -764    24, ΔH.sub.r *(298 K.) =                                                 -1372 kJ mol.sup.-1                                 and                                                                            [II-871]                                                                             ZnCl.sub.2 (cr) + 8 F(g) → ZnF.sub.2 (cr) + 2 ClF.sub.3 (g)       -415      8 × 79                                                                            -764    2 × -159, ΔH.sub.r.sup.0 (298 K.)                                  =                                                                              -1299 kJ mol.sup.-1                                 -369      8 × 62                                                                            -713    2 × -119, ΔG.sub.r.sup.0 (298 K.)                                  =                                                                              -1078 kJ mol.sup.-1.                                ______________________________________                                    

It should be noted that although O+F* is an effective procedure, F* is not since it will not volatilize ZnF₂ !

    ______________________________________                                         [II-872]                                                                             Zn(cr) + 2 CH.sub.3 (g) → (CH.sub.3).sub.2 Zn(l)                  0          2 × 146                                                                           23, ΔH.sub.r.sup.0 (298 K.) =                                            -269 kJ mol.sup.-1,                                        [II-873]                                                                             ZnO(cr) + 4 CH.sub.3 (g) → (CH.sub.3).sub.2 Zn(l)                       + (CH.sub.3).sub.2 O(g)                                                  -348       4 × 146                                                                           23     -184, ΔH.sub.r.sup.0 (298 K.) =                                          -397 kJ mol.sup.-1,                                 [II-874]                                                                             ZnCl.sub.2 (cr) + 4 CH.sub.3 (g) → (CH.sub.3).sub.2 Zn(l) +             2 CH.sub.3 Cl(g)                                                         -415       4 × 146                                                                           23     2 × -84, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -314 kJ mol.sup.-1                                  and                                                                            [II-875]                                                                             ZnF.sub.2 (cr) + 4 CH.sub.3 (g) → (CH.sub.3).sub.2 Zn(l) + 2            CH.sub.3 F(g)                                                            -764       4 ×  146                                                                          23     2 × -234, ΔH.sub.r.sup.0 (298 K.)                                  =                                                                              -265 kJ mol.sup.-1.                                 ______________________________________                                    

Thus, we have the choice of four procedures for the volatilization of the zinc species:

O+F*

O+CH₃

F+CH₃

CH₃.

3. CADMIUM

    ______________________________________                                         [II-876]                                                                             Cd(cr) + O(g) → CdO(cr)                                           0         249      -258, ΔH.sub.r.sup.0 (298 K.) =                                          -507 kJ mol.sup.-1                                          0         232      -228, ΔG.sub.r.sup.0 (298 K.) =                                          -460 kJ mol.sup.-1,                                         [II-877]                                                                             CdCl.sub.2 (cr) + 5 O(g) → CdO(cr) + 2 ClO.sub.2 (g)              -392      5 × 249                                                                           -258    2 × 102, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -907 kJ mol.sup.-1                                  -344      5 × 232                                                                           -228    2 × 120, ΔG.sub.r.sup.0 (298 K.)                                   =                                                                              -804 kJ mol.sup.-1                                  and                                                                            [II-878]                                                                             CdF.sub.2 (cr) + 5 O(g) → CdO(cr) + 2 FO.sub.2 (g)                -700      5 × 249                                                                           -258    2 × 13, ΔH.sub.r.sup.0 (298 K.) =                                  -777 kJ mol.sup.-1                                  - 648     5 × 232                                                                           -228    2 × 27, ΔG.sub.r.sup.0 (298 K.) =                                  -686 kJ mol.sup.-1.                                 [II-879]                                                                             Cd(cr) + 2 F(g) → CdF.sub.2 (cr)                                  0         2 × 79                                                                            -700, ΔH.sub.r.sup.0 (298 K.) =                                          -858 kJ mol.sup.-1                                          0         2 × 62                                                                            -648, ΔG.sub.r.sup.0 (298 K.) =                                          -772 kJ mol.sup.-1,                                         [II-880]                                                                             Cd(cr) + 2 F*(g) → CdF.sub.2 (cr)                                 0         2 × 245                                                                           -700, ΔH.sub.r *(298 K.) =                                               -1190 kJ mol.sup.-1,                                        [II-881]                                                                             CdO(cr) + 4 F(g) → CdF.sub.2 (cr) + OF.sub.2 (g)                  -258      4 × 79                                                                            -700    24, ΔH.sub.r.sup.0 (298 K.) =                                            -734 kJ mol.sup.-1                                  -228      4 × 62                                                                            -648    42, ΔG.sub.r.sup.0 (298 K.) =                                            -626 kJ mol.sup.-1,                                 [II-882]                                                                             CdO(cr) + 4 F*(g) → CdF.sub.2 (cr) + OF.sub.2 (g)                 -258      4 × 245                                                                           -700    24, ΔH.sub.r *(298 K.) =                                                 -1398 kJ mol.sup.-1                                 and                                                                            [II-883]                                                                             CdCl.sub.2 (cr) + 8 F(g) → CdF.sub.2 (cr) + 2 ClF.sub.3 (g)       -392      8 × 79                                                                            -700    2 × -159, ΔH.sub.r.sup.0 (298 K.)                                  =                                                                              -1258 kJ mol.sup.-1                                 -344      8 × 62                                                                            -648    2 × -119, ΔG.sub.r.sup.0 (298 K.)                                  =                                                                              -1038 kJ mol.sup.-1.                                [II-884]                                                                             Cd(cr) + 2 CH.sub.3 (g) → (CH.sub.3).sub.2 Cd(l)                  0         2 × 146                                                                           64, ΔH.sub.r.sup.0 (298 K.) =                                            -228 kJ mol.sup.-1                                          0         2 × 148                                                                           139, ΔG.sub.r.sup.0 (298 K.) =                                           -157 kJ mol.sup.-1,                                         [II-885]                                                                             CdO(cr) + 4 CH.sub.3 (g) → (CH.sub.3).sub.2 Cd(l)                       + (CH.sub.3).sub.2 O(g)                                                  -258      4 × 146                                                                           64      -184, ΔH.sub.r.sup.0 (298 K.) =                                          -446 kJ mol.sup.-1                                  -228      4 × 148                                                                           139     -113, ΔG.sub.r.sup.0 (298 K.) =                                          -338 kJ mol.sup.-1,                                 [II-886]                                                                             CdCl.sub.2 (cr) + 4 CH.sub.3 (g) → (CH.sub.3).sub.2 Cd(l) +             2 CH.sub.3 Cl(g)                                                         -392      4 × 146                                                                           64      2 × -84, ΔH.sub.r.sup.0 (298 K.)                                   =                                                                              -296 kJ mol.sup.-1                                  -344      4 × 148                                                                           139     2 × -60, ΔG.sub.r.sup.0 (298 K.)                                   =                                                                              -229 kJ mol.sup.-1                                  and                                                                            [II-887]                                                                             CdF.sub.2 (cr) + 4 CH.sub.3 (g) → (CH.sub.3).sub.2 Cd(l) + 2            CH.sub.3 F(g)                                                            -700      4 × 146                                                                           64      2 × -234, ΔH.sub.r.sup.0 (298 K.)                                  =                                                                              -288 kJ mol.sup.-1                                  -648      4 × 148                                                                           139     2 × -210, ΔG.sub.r.sup.0 (298 K.)                                  =                                                                              -225 kJ mol.sup.-1.                                 ______________________________________                                    

Again we have the choice of four procedures:

O+F*

O'CH₃

F+CH₃

CH₃.

4. MERCURY

    __________________________________________________________________________     [II-888]                                                                           Hg(l) + O(g) → HgO(cr)                                              0          249                                                                               -91,   ΔH.sub.r.sup.0 (298 K.) = -340 kJ mol.sup.-1,       0          232                                                                               -58,   ΔG.sub.r.sup.0 (298 K.) = -290 kJ mol.sup.-1,       [II-889]                                                                           Hg(l) + O*(g) → HgO(cr)                                             0          529                                                                               -91,   ΔH.sub.r *(298 K.) = -620 kJ mol.sup.-1,            [II-890]                                                                           0.5 Hg.sub.2 Cl.sub.2 (cr) + 3 O(g) → HgO(cr) + ClO.sub.2 (g)       0.5 × -265                                                                          3 × 249                                                                       -91                                                                               102, ΔH.sub.r.sup.0 (298 K.) = -604 kJ                                        mol.sup.-1                                             0.5 × -210                                                                          3 × 232                                                                       -58                                                                               120, ΔG.sub.r.sup.0 (298 K.) = -529 kJ                                        mol.sup.-1,                                            [II-891]                                                                           HgCl.sub.2 (cr) + 4 O(g) → HgO(cr) + 2 ClO.sub.2 (g)                -230       4 ×  249                                                                      -91                                                                               2 × 102,                                                                      ΔH.sub.r.sup.0 (298 K.) = -653 kJ                                        mol.sup.-1                                             -184       4 × 232                                                                       -58                                                                               2 × 120,                                                                      ΔG.sub.r.sup.0 (298 K.) = -562 kJ                                        mol.sup.-1,                                            [II-892]                                                                           0.5 Hg.sub.2 F.sub.2 (cr) + 3 O(g) → HgO(cr) + FO.sub.2 (g)         0.5 × -485                                                                          3 × 249                                                                       -91                                                                               13,  ΔH.sub.r.sup.0 (298 K.) = -582 kJ                                        mol.sup.-1                                             0.5 × -469                                                                          3 × 232                                                                       -58                                                                               27,  ΔG.sup.0 (298 K.) = -492 kJ mol.sup.-1           and                                                                            [II-893]                                                                           HgF.sub.2 (cr) + 5 O(g) → HgO(cr) + 2 FO.sub.2 (g)                  -423       5 × 249                                                                       -91                                                                               2 × 13,                                                                       ΔH.sub.r.sup.0 (298 K.) = -887 kJ                                        mol.sup.-1                                             -374       5 × 232                                                                       -58                                                                               2 × 27,                                                                       ΔG.sub.r.sup.0 (298 K.) = -790 kJ                                        mol.sup.-1.                                            [II-894]                                                                           Hg(l) + F(g) → 0.5 Hg.sub.2 F.sub.2 (cr)                            0          79 0.5 × -485,                                                                     ΔH.sub.r.sup.0 (298 K.) = -322 kJ mol.sup.-1        0          62 0.5 × -469,                                                                     ΔG.sub.r.sup.0 (298 K.) = -296 kJ mol.sup.-1,       [II-895]                                                                           Hg(l) + F*(g) → 0.5 Hg.sub.2 F.sub.2 (cr)                           0          245                                                                               0.5 × -485,                                                                     ΔH.sub.r *(298 K.) = -488 kJ mol.sup.-1,            [II-896]                                                                           0.5 Hg.sub.2 F.sub.2 (cr) + F(g) → HgF.sub.2 (cr)                   0.5 × -485                                                                          79 -423,  ΔH.sub.r.sup.0 (298 K.) = -260 kJ mol.sup.-1        0.5 × -469                                                                          62 -374,  ΔG.sub.r.sup.0 (298 K.) = -202 kJ mol.sup.-1        and                                                                            [II-897]                                                                           0.5 Hg.sub.2 F.sub.2 (cr) + F*(g) → HgF.sub.2 (cr)                  0.5 × -485                                                                          245                                                                               -423,  ΔH.sub.r *(298 K.) = -426 kJ                        __________________________________________________________________________                          mol.sup.-1.                                          

Thus, although monofluorine will convert mercury to mercurous fluoride and mercurous fluoride to mercuric fluoride, even with excited state monofluorine the reactions are not sufficiently energetic to volatilized the product fluorides. We should, however, consider the reaction between monofluorine and the oxide.

    ______________________________________                                         [II-898]                                                                             HgO(cr) + 4 F(g) → HgF.sub.2 (cr) + OF.sub.2 (g)                  -91      4 × 79                                                                           -423    24, ΔH.sub.r.sup.0 (298 K.) = -624 kJ                                    mol.sup.-1                                            -58      4 × 62                                                                           -374    42, ΔG.sub.r.sup.0 (298 K.) = -522 kJ                                    mol.sup.-1.                                           ______________________________________                                    

Since monoxygen cannot volatilize the oxide, by itself it is not a satisfactory volatilizing reagent. Similarly, by itself monofluorine is not a satisfactory volatilizing reagent. The procedure O+F, however, is satisfactory.

    __________________________________________________________________________     [II-899]                                                                           Hg(l) + 2 CH.sub.3 (g) → (CH.sub.3).sub.2 Hg(l)                     0     2 × 146                                                                        60, ΔH.sub.r.sup.0 (298 K.) = -232 kJ mol.sup.-1             0     2 × 148                                                                       140, ΔG.sub.r.sup.0 (298 K.) = -156 kJ mol.sup.-1,            [II-900]                                                                           HgO(cr) + 4 CH.sub.3 (g) → (CH.sub.3).sub.2 Hg(l)                       + (CH.sub.3).sub.2 O(g)                                                    -91     4 × 146                                                                       60   -184, ΔH.sub.r.sup.0 (298 K.) = -617 kJ                                        mol.sup.-1                                             -58     4 × 148                                                                       140  -113, ΔG.sub.r.sup.0 (298 K.) = -507 kJ                                        mol.sup.-1,                                            [II-901]                                                                           Hg.sub.2 Cl.sub.2 (cr) + 6 CH.sub.3 (g) → 2 (CH.sub.3).sub.2            Hg(l) + 2 CH.sub.3 Cl(g)                                                   -265    6 × 146                                                                       2 × 60                                                                        2 × -84,                                                                       ΔH.sub.r.sup.0 (298 K.) = -659 kJ                                        mol.sup.-1                                             -210    6 × 148                                                                       2 × 140                                                                       2 × -60,                                                                       ΔG.sub.r.sup.0 (298 K.) = -518 kJ                                        mol.sup.-1,                                            [II-902]                                                                           HgCl.sub.2 (cr) + 4 CH.sub.3 (g) → (CH.sub.3).sub.2 Hg(l) + 2           CH.sub.3 Cl(g)                                                             -230    4 × 146                                                                       60   2 × -84,                                                                       ΔH.sub.r.sup.0 (298 K.) = -462 kJ                                        mol.sup.-1                                             -184    4 × 148                                                                       140  2 × -60,                                                                       ΔG.sub.r.sup.0 (298 K.) = -388 kJ                                        mol.sup.-1,                                            [II-903]                                                                           Hg.sub.2 F.sub.2 (cr) + 6 CH.sub.3 (g) → 2 (CH.sub.3).sub.2             Hg(l) + 2 CH.sub.3 F(g)                                                    -485    6 × 146                                                                       2 × 60                                                                        2 × -234,                                                                      ΔH.sub.r.sup.0 (298 K.) = -739 kJ                                        mol.sup.-1                                             -469    6 × 148                                                                       2 × 140                                                                       2 ×  -210,                                                                     ΔG.sub.r.sup.0 (298 K.) = -559 kJ                                        mol.sup.-1                                             and                                                                            [II-904]                                                                           HgF.sub.2 (cr) + 4 CH.sub.3 (g) → (CH.sub.3)2 Hg(l) + 2                 CH3F(g)                                                                    -423    4 × 146                                                                       60   2 × -234,                                                                      ΔH.sub.r.sup.0 (298 K.) = -569 kJ                                        mol.sup.-1                                             -374    4 × 148                                                                       140  2 × -210,                                                                      ΔG.sub.r.sup.0 (298 K.) = -498 kJ                                        mol.sup.-1.                                            __________________________________________________________________________

Thus, methyl by itself is an effective volatilizing reagent.

R. Summary of Transition Metals Chemistries

In SECTION IX.H. we received the chemistries for the Main Group elements. The recommended general procedures are

    (H).sub.a +O/NO.sub.2 +F+CH.sub.3 +(H).sub.b,[II-905]

where

a. monohydrogen is used as the first reagent if a large quantity of fluorocarbons is present, and

b. monohydrogen is used as the last reagent if only a small quantity of fluorocarbons is present.

In the absence of thermodynamic data on the nitrates except for the lanthanides no comments can be made with respect to O/NO₂. We have found CO or CO* to be a useful reagent in many cases and essential for rhodium. In addition, we have found hfa essential for palladium and monochlorine essential for gold.

Summarizing the procedures for the various elements we have:

    ______________________________________                                         Sc          O + F*   H + F                                                     Y           O + F*   H + F*                                                    Lanthanides O/NO.sub.2 + F, O + F*, H + F                                      Ti          O + F,   H + F                                                     Zr          O + F,   H + F                                                     Hf          O + F,   H + F                                                     V           O + F, F, O + CO, CO                                               Nb          O + F, F                                                           Ta          O + F,   O + CH.sub.3, CH.sub.3                                    Cr          O + F,   O + CO, CO*                                               Mo          O + F, F, O + CO, CO*                                              W           O + F, F, O + CO*, O + CH.sub.3, CH.sub.3                          Mn          O + F,   O + CO, CO*                                               Re          O + F,   O + CO, CO*                                               Fe          O + F,   O + CO, CO*                                               Co          O + F,   O + CO, CO*                                               Ni          O + F*,   O + CO, CO*                                              Ru          O + F,   O + CO, CO*                                               Rh                O + CO*, CO*                                                 Pd                hfa                                                          Os          O,      CO*                                                        Ir          O + F, F, O + CO, CO                                               Pt          O + F, F, hfa                                                      Cu          O + F*    hfa                                                      Ag          NO RECOMMENDATION                                                  Au                Cl                                                           Zn          O + F*   O + CH.sub.3, F + CH.sub.3, CH.sub.3                      Cd          O + F*   O + CH.sub.3, F + CH.sub.3, CH.sub.3                      Hg          O + F,   CH.sub.3.                                                 ______________________________________                                    

In order to accommodate Sc, Y and Cu we change F in [II-905] to F*. In order to accommodate Rh we add CO*. For Pd we add hfa, and for Au we add Cl. Thus, the general recommended procedures for the entire Periodic Table are

    (H).sub.a +O/NO.sub.2 +F*+CH.sub.3 +CO*+hfa+Cl+(H).sub.b.[II-906]

These procedures are for wafer cleaning. For film etching a specific procedure has to be chosen in accordance with the other materials present.

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<I-25> Ref. <I-17>, pp. 1665-1666.

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<II-13> Ref. <II-3>, p. 1094.

<II-14> Ref. Eugene S. Domalski and Elizabeth D. Hearing `Estimation of the Thermodynamic Properties of Hydrocarbons at 298.15K`, J. Phys. Chem. Ref. Data, 1988, 17 (4), 1664-1665.

<II-15> Ref. G. Pilcher and H. A. Skinner, `Thermochemistry of Organometallic Compounds`, in Frank R Hartley and Saul Patai, eds., The Chemistry of the Metal-Cargon Bond, Vol. 1., John Wiley & Sons, Ltd., Chichester (1982 ) , pp. 43-90.

<II-16> Jindrich Leitner, Cestmir Cerny, Petr Vonka and Jan Mikulec, `Theoretical and Experimental Study of Chemical Equilibrium in the Systems Si-Cl and Si-Cl-H. Calculation of Chemical Equilibrium in the Systems Si-Cl and Si-Cl-H`, Collection of Czechoslovak Chemical Communications, 1989, 54 (11), 2899.

<II-17> I. Barin, O. Knacke and O. Kubaschewski Thermochemical Properties of Inorganic Substances, Supplement, Springer-Verlag, Berlin (1977), p. 89.

<II-18> _(A) I. Barin and O. Knacke, Thermochemical Properties of Inorganic Substances, Springer-Verlag, Berlin (1973), p. 394.

<II-19> Ref. <II-17>, p. 351.

<II-20> Ref. <II-17>, p. 155.

<II-21> Ref. <II-17>, p. 450.

<II-22> Ref. <II-17>, p. 310.

<II-23> C. E. Wicks and F. E. Block, Thermodynamic Properties of 65 Elements--Their Oxides, Halides, Carbides, and Nitrides, Bulletin 605, Bureau of Mines (1963).

<II-24> Ref. <II-17>, pp. 351, 155, 450, 310.

<II-25> G. G. Libowitz and A. J. Maeland, `Hydrides`,in Karl A. Gschneidner Jr., and LeRoy Eyring, Handbook on the Physics and Chemistry of Rare Earths, Vol. 3, North-Holland Publishing Company, Amsterdam (1979), p. 309.

<II-26> Ref. <C>, pp. 4-127, 4-83 and 4-117.

<II-27> G. Dittmer and U. Niemann, `Heterogeneous Reactions and Chemical Transport of Tungsten with Halides and Oxygen Under Steady-State Conditions of Incandescent Lamps`, Philips J. Res., 1981, 36, 89-113.

<II-28> Ref. A. A. Woolf, `An Outline of Rhenium Chemistry`, Quarterly Reviews, 1961, 15 (3), 386.

<II-29> Ref. <II-17>, p. 535.

<II-30,> Keith G. G. Hopkins and Peter G. Nelson, `Comparison of the Thermochemistry of Difluorides and Potassium Hexaflorometallates (iv) of the Elements of the Germanium Triad with that of the Elements of the Nickel Triad: A Study of the Inert-pair Effect`, J. Chem. Soc., Dalton Trans., 1984, 1393.

<II-31> A. A. Bondarenko, M. V. Korobov, O. L. Sharova, A. V. Ryzhov and L. N. Sideroy, `Mass Spectral Study of Equilibrium with Participation of Higher Platinum Fluorides`, Zh. Neorg. Kahim., 1987, 32 (1), 28.

<II-32> M. V. Korobov, V. V. Nikulin, N. S. Chilingarov and L. N. Siderov, `Enthalpy of Formation of Platinum Hexafluoride`, J. Chem. Thermodynamics, 1986, 18 (3), 235.

<II-33> Manuel A. V. Ribeiro da Silva, `Thermochemistry of β-Diketones and Metal-β-Diketones, Metal-Oxygen Bond Enthalpies`, in Manuel A. V. Ribeiro da Silva, ed., Thermo-Chemistry and Its Applications to Chemical and Biochemical Systems, D. Reidel Publishing Company, Dordrecht (1984), pp. 317-338.

<II-34> Ref. A. F. Wells, Structural Inorganic Chemistry, 5th ed., Clarendon Press, Oxford (1984), 540-543.

<II-35> E. W. Berg and F. R. Hartlage, `Fractional Sublimation of Various Acetylacetonates`, Anal. Chim. Acta, 1965, 33 (2), 173-81.

<II-36 > Aesar Catalog, 1989-21990, Johnson Matthey, Seabrook, N.H., p. 181.

<II-37> Susan Budavari, ed., The Merck Index, 11th ed., Merck & Co., Inc., Rahway, N.J. (1989 ) , pp. 710-1.

Industrial Applicability

The present invention provides VFFTE apparatus, methods and chemistries for wafer fabrication and related technologies. It features relatively fast reactions at low temperatures and with minimal human handling of the wafers. Thereby wafer throughput can be greatly increased.

While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modification, and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice in the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as fall within the scope of the invention and the limits of the appended claims. 

That which is claimed is:
 1. An apparatus for providing a reactive radical species at a substrate surface, comprising:a wall structure defining an interior chamber; mounting means for mounting a substrate in the chamber at a target position therein with a surface region of the substrate oriented in a selected direction; first vaporous chemical introducing means for introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface region of the substrate; first radical species generating means intermediate the first vaporous chemical introducing means and the substrate surface region for generating a first radical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species with the first radical species flowing toward the surface region of the substrate; and pumping means for evacuating the chamber and for maintaining a pressure within the chamber of ≦10⁻⁷ Torr during the introduction of the first vaporous chemical.
 2. An apparatus as set forth in claim 1, further including:second vaporous chemical introducing means for introducing a second vaporous chemical to the chamber intermediate the first radical species generating means and the surface region of the substrate with the second vaporous chemical flowing toward the surface region of the substrate, the second vaporous chemical being selected to react with substantially all of the first radical species to produce a second radical species flowing toward the surface region of the substrate, or to dilute the first radical species.
 3. An apparatus as set forth in claim 1, wherein the first radical species generating means comprises a microwave generator.
 4. An apparatus as set forth in claim 3, wherein the first radical species generating means further comprises an electron source.
 5. An apparatus as set forth in claim 3, wherein the first radical species generating means further comprises a defocussed electron gun.
 6. An apparatus as set forth in claim 1, wherein the first radical species generating means comprises an electron source.
 7. An apparatus as set forth in claim 1, wherein the first radical species generating means comprises a defocussed electron gun.
 8. An apparatus as set forth in claim 1, wherein the first radical species generating means comprises a defocussed tunable laser.
 9. An apparatus as set forth in claim 1, wherein the first radical species generating means comprises a plurality of defocussed tunable lasers.
 10. An apparatus as set forth in claim 1, wherein the orientation of the substrate surface region, the first vaporous chemical introducing means and the first radical species generating means is such as to provide a substantially uniform distribution of the first radical species over the surface region of the substrate.
 11. An apparatus as set forth in claim 2, wherein the orientation of the substrate surface region, the first vaporous chemical introducing means, the first radical species generating means and the second vaporous chemical introducing means is such as to provide a substantially uniform distribution of the second radical species over the surface region of the substrate.
 12. An apparatus as set forth in claim 1, wherein the chamber, where the substrate is mounted, is at least about three times the width of the largest dimension of the surface region.
 13. A method of producing a radical species which can carry out a chemical reaction adjacent the surface of a substrate, comprising:mounting a substrate in a sealed chamber at a target position therein with a surface region of the substrate oriented in a selected direction; introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface region of the substrate; generating a first radical species from the first vaporous chemical at a position in the chamber intermediate the place of introduction of the vaporous chemical and the surface region of the substrate without producing significant amounts of ionized species with the first radical species flowing toward the surface region of the substrate; and evacuating the chamber at a rate sufficient for maintaining a pressure within the chamber of 10⁻⁷ Torr or below during the introduction of the first vaporous chemical.
 14. A method as set forth in claim 13, further including:introducing a second vaporous chemical to the chamber intermediate the position of generation of the first radical species and the surface region of the substrate with the second vaporous chemical flowing toward the surface region of the substrate, the second vaporous chemical being selected to react with substantially all of the first radical species to produce a second radical species flowing toward the surface region of the substrate.
 15. A method as set forth in claim 13, wherein the orientation of the substrate surface region, the geometry of the first vaporous chemical introducing and the geometry of the first radical species generating is such as to provide a substantially uniform distribution of the first radical species over the surface region of the substrate.
 16. A method as set forth in claim 14, wherein the orientation of the substrate surface region, the geometry of the first vaporous chemical introducing, the geometry of the first radical species generating and the geometry of the second vaporous chemical introducing is such as to provide a substantially uniform distribution of the second radical species over the surface region of the substrate.
 17. A method of cleaning a surface of a substrate to remove one or more solids from a surface thereof, comprising:generating a neutral activated chemical species without generating a substantial quantity of ionized activated species at a pressure of no more than about 0.1 Torr within a sealed evacuatable chamber; flowing the neutral activated chemical species against the surface, the neutral activated chemical species being selected to react with and convert at least one of the solids to a vaporous species; and evacuating the chamber at an evacuatiion rate sufficient to maintain the pressure therein at ≦10⁻⁷ Torr during the flowing until a desired quantity of the solid has been removed by vaporization.
 18. A method as set forth in claim 17, wherein the solid comprises a layer of a different chemical composition from the surface, the layer covering the majority of the surface.
 19. A method as set forth in claim 17, wherein the solid comprises a plurality of particles lying upon the surface.
 20. A method as set forth in claim 17, wherein the generating and flowing steps comprise:introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface; and irradiating the first vaporous chemical to produce the neutral activated chemical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species.
 21. A method as set forth in claim 17, wherein the generating and flowing steps comprise:introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface; irradiating the first vaporous chemical to produce a first activated chemical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species; introducing a second vaporous chemical to the chamber intermediate the site of introduction of the first vaporous chemical and the surface with the second vaporous chemical flowing toward the surface, the second vaporous chemical being selected to react with substantially all of the first activated chemical species to produce the neutral chemical activated species flowing toward the surface.
 22. A method of etching into a surface of a substrate, comprising:generating a neutral activated chemical species without generating a substantial quantity of ionized activated species at a pressure of no more than about 0.1 Torr within a sealed evacuatable chamber; flowing the neutral activated chemical species against the surface, the neutral activated chemical species being selected to react with and convert the surface to a vaporous species until a desired quantity of the surface has been removed by vaporization; and evacuating the chamber at an evacuation rate sufficient to maintain the pressure therein at ≦10⁻⁷ Torr during the flowing until a desired quantity of the surface has been removed by vaporization.
 23. A method as set forth in claim 22, wherein the generating and flowing steps comprise:introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface; and irradiating the first vaporous chemical to produce the neutral activated chemical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species.
 24. A method as set forth in claim 22, wherein the generating and flowing steps comprise:introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface; irradiating the first vaporous chemical to produce a first activated chemical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species; introducing a second vaporous chemical to the chamber intermediate the site of introduction of the first vaporous chemical and the surface with the second vaporous chemical flowing toward the surface, the second vaporous chemical being selected to react with substantially all of the first activated chemical species to produce the neutral chemical activated species flowing toward the surface.
 25. A method as set forth in claim 24, further including, prior to the generating step:positioning a protective mask over selected portions of the surface, the mask being of a construction such that only those portions of the surface which are not covered by the mask are etched by the neutral activated chemical species.
 26. A method as set forth in claim 25, wherein the generating and flowing steps comprise:introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface; and irradiating the first vaporous chemical to produce the neutral activated chemical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species.
 27. A method as set forth in claim 25, wherein the generating and flowing steps comprise:introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface; irradiating the first vaporous chemical to produce a first activated chemical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species; introducing a second vaporous chemical to the chamber intermediate the site of introduction of the first vaporous chemical and the surface with the second vaporous chemical flowing toward the surface, the second vaporous chemical being selected to react with substantially all of the first activated chemical species to produce the neutral chemical activated species flowing toward the surface.
 28. A method as set forth in claim 24, wherein the generating and flowing steps comprise:introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface; and irradiating the first vaporous chemical to produce the neutral activated chemical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species.
 29. A method as set forth in claim 24, wherein the generating and flowing steps comprise:introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface; irradiating the first vaporous chemical to produce a first activated chemical species from the first vaporous chemical at a pressure of no more than about 0.1 Torr without producing significant amounts of ionized species; introducing a second vaporous chemical to the chamber intermediate the site of introduction of the first vaporous chemical and the surface with the second vaporous chemical flowing toward the surface region of the substrate, the second vaporous chemical being selected to react with substantially all of the first activated chemical species to produce the neutral chemical activated species flowing toward the surface.
 30. A method as set forth in claim 29, wherein the substrate comprises a semiconductor wafer.
 31. A method as set forth in claim 30, wherein the irradiating is by one or more of microwaves, defocussed electron guns and defocussed tunable lasers.
 32. A method as set forth in claim 31, further including:monitoring the composition of the gaseous species being evacuated from the chamber; and controlling how much of the layer is removed based upon the monitoring.
 33. A method of depositing a chemical species adjacent a surface region of a substrate, comprising:mounting a substrate in a sealed chamber at a target position therein with the surface region of the substrate oriented in a selected direction; introducing a first vaporous chemical to the chamber with the first vaporous chemical flowing toward the surface region of the substrate; generating a first radical species from the first vaporous chemical at a position in the chamber intermediate the place of introduction of the vaporous chemical and the surface region of the substrate without producing significant amounts of ionized species with the first radical species flowing toward the surface region of the substrate; evacuating the chamber at a rate sufficient for maintaining a pressure within the chamber of 10⁻⁷ Torr or below during the introduction of the first vaporous chemical; introducing a second vaporous chemical to the chamber intermediate the position of generation of the first radical species and the surface region of the substrate with the second vaporous chemical flowing toward the surface region of the substrate, the second vaporous chemical being selected to react with the first radical species such that substantially all of the second vaporous chemical reacts with the first radical species to produce a second radical species flowing toward the surface region of the substrate, the second radical species, on contacting the surface region of the substrate, depositing the chemical species adjacent the surface region of the substrate.
 34. A method as set forth in claim 33, wherein the orientation of the substrate surface region, the geometry of the first vaporous chemical introducing, the geometry of the first radical species generating and the geometry of the second vaporous chemical introducing is such as to provide a substantially uniform distribution of the second radical species over the surface region of the substrate. 